TW200423109A - Optical disc having hard-coating layer to which surface lubricity is imparted - Google Patents

Optical disc having hard-coating layer to which surface lubricity is imparted Download PDF

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TW200423109A
TW200423109A TW092132332A TW92132332A TW200423109A TW 200423109 A TW200423109 A TW 200423109A TW 092132332 A TW092132332 A TW 092132332A TW 92132332 A TW92132332 A TW 92132332A TW 200423109 A TW200423109 A TW 200423109A
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group
formula
optical disc
layer
mass
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TW092132332A
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Chinese (zh)
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Satoshi Kondo
Toshihiko Higuchi
Hirotsugu Yamamoto
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Asahi Glass Co Ltd
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24306—Metals or metalloids transition metal elements of groups 3-10
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B2007/25705—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G11B2007/2571—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials containing group 14 elements except carbon (Si, Ge, Sn, Pb)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B2007/25705—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G11B2007/25713—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials containing nitrogen
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
    • G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/256—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers improving adhesion between layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/258—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers
    • G11B7/2585—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers based on aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/21—Circular sheet or circular blank

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

In an optical disc of a type where a laser beam is radiating on a recording layer through a thin-film cover layer, on the surface ofthe thin-film cover layer, a hard-coating layer is formed of a hardened covering formed of cured composition cured by active energy beam, which comprises a polymerizable monomer (A), colloidal silica (B), an imparting lubrication agent (C ), an active energy beam polymerization initiator (D). The lubricity imparting agent (C ) contains a lubricity imparting agent (C-T) having, in a molecular, a portion (c-1), a portion (c-2) excellent in dissolubility with the polymerizable monomer, and an active energy beam curing functional group (c-3). The hard-coating layer formed on the thin-film cover layer of the optical disc of the present invention is excellent in wear-resistance, transparency, and long-term surface lubricity superiority.

Description

200423109 (1) 玖、發明說明 【發明所翳之技術領域】 本發明係關於在磁碟基板之表面，記錄層及薄膜表層 爲依此順序層合者，使用於資料之記錄及/或播放之雷射 光通過薄膜表層而照射於記錄層方式之光碟中，在薄膜表 層之表面進而形成耐磨損性，透明性，長期之表面潤滑性 優異之硬塗層的光碟。 【先前技術】 近年來，相對應於多媒體化，將大量資料以高密度且 迅速地記錄，且迅速地播放之光記錄裝置廣受注目。於此 方式之光記錄裝置，如光碟（CD)，雷射光碟（LD) 般在磁碟製作時，預先將資料在磁碟上壓印（stamping ) 使得僅有情報播放爲可能之播放 用型磁碟上之情報予以 播放者、··或如C D - R般，僅可記錄資料一次之CD-R磁 碟予以記錄資料，將該記錄之資料予以播放者，使用光磁 記錄方式或相變化記錄方式可將多次資料重覆讀寫消去之 重覆讀寫型磁碟予以記錄資料，將該記錄之資料予以播放 者等。在該等光記錄裝置，資料之記錄及播放係使用將雷 射光以透鏡集中於繞射限界爲止之光點來進行。此光點之 大小，係以雷射光之波長爲λ，透鏡之開口數爲N A，則 爲λ/ΝΑ之程度（角田義人監修，「光碟存儲 (storage )存儲之基礎與應用」，社團法人電子情報通信 學會，1 99 5 年，ρ·65 )。 (2) (2)200423109 要記錄更高密度之資料，亦即，要使更小之凹點圖案 (pit pattern )在光記錄媒體上形成，則有必要使光點更 小。爲了使光點（p h 〇 t 〇 s ρ 〇 t )之尺寸變小，可考慮由上 式使雷射光波長（λ )變短之方法，或使透鏡開口數（ N A )變大之方法二種。現在所使用光碟用半導體雷射之 波長主爲780〜680 nm，更短波長之650 nm之橙色雷 射，進而使用短波長之綠，藍色雷射光等，正被檢討中。 尤其是使用藍色雷射之方式方面，將光源波長爲400 n m左右，N A爲0·6以上’來獲得更大記錄密度者被提 案出。但是，由於光源之短波長化或對物透鏡之高N A 化，光碟面相對於光軸，自垂直偏離角度（傾斜角（t i 11 angle))之容許量（tolerance dose)或光碟之厚度不均 勻之容許量會變小。 該等容許量變小之理由，係因爲在光碟傾斜角之情形 會產生慧形像差，而在光碟之厚度不均勻之情形會產生球 面像差，使得光學頭裝置之集光特性劣化，信號之讀取變 的困難。 習知之光碟（CD)等，可設於記錄層表面之表層厚 度爲1.2 mm，而在數位多媒體光碟（DVD)等該厚度爲 〇·6 mm，各自之磁碟基板自體擔任表層角色，通過磁碟 基板而在記錄層照射雷射光。但是，在使用藍色雷射之方 式，爲了可使透鏡之開口數（N A )變大，並使上述傾斜 之容許量或光碟之厚度不均勻之容許量至少有所作用，有 必要使表層厚度薄至〇 .1 m m左右。因此，如習知之光碟 -6 - (3) (3)200423109 般在基板自體要擔任表層角色爲不可能，在藍色雷射之方 式’係在形成記錄層（反射膜，記錄膜等之層合膜）等之 表面形成厚度 0.1mm左右之薄膜表層，通過該薄膜表 層，在層合膜照射雷射光。 但是，使用如藍色雷射般之短波長雷射之情形，光學 頭與光碟之間隔小至0.1〜0.2mm左右。在光記錄裝置， 爲達成高資料轉移率（transfer rate )，有必要使光碟在 極高速下旋轉，藉由所使用之雷射光波長，透鏡之開口數 (NA)，磁碟之記錄容量及所期望之資料轉移率之組 合，使得光碟之最大旋轉速度可達2500 r p m以上，視 情況亦可達到5 000 r p m以上。在光學頭與光碟之間隔 係如上述，於非常狹小之狀態下，使光碟在此等高速旋 轉，可使光學頭有接觸光碟之可能性，而在覆蓋記錄層表 面之薄膜表層被要求高度耐磨損性。 又，在使用更短波長之雷射時，在光碟之雷射光入射 面產生之刮傷或塵埃之附著，則與記錄及播放時之誤差 (error )大有關係。因此，爲防止此種記錄及播放時之誤 差，則在成爲雷射光入射面之薄膜表層，漸被要求更進一 步之耐磨損性。 薄膜表層隨著耐磨損性之添加，以具有表面潤滑性爲 佳。薄膜表層在耐磨損性方面雖優異，但表面潤滑性差， 作用於磁碟之摩擦力絶對値變大，同時摩擦力之變動亦變 大。此時，磁碟旋轉變成不穩定，會有記錄誤差或軌跡誤 差（t r a c k i n g e r r 〇 r )產生之情形。 (4) 200423109 賦與對薄膜表層之表面潤滑性則有助於該薄膜表層耐 磨損性之提高。在薄膜表層表面賦與表面潤滑性時，由於 所添加之外力錯開，因而造成耐磨損性提高。200423109 (1) Description of the invention [Technical field of invention] The present invention relates to a surface of a magnetic disk substrate, a recording layer and a film surface layer laminated in this order, and is used for recording and / or playing back data. Laser light passes through the surface layer of the film and irradiates the disc with the recording layer method. On the surface of the surface layer of the film, a hard-coated disc with excellent abrasion resistance, transparency, and long-term surface lubricity is formed. [Prior Art] In recent years, corresponding to multimedia, optical recording devices that record a large amount of data at high density and quickly, and quickly play back, have attracted wide attention. In this way, the optical recording device, such as a compact disc (CD) or a laser disc (LD), stamps data on the disc in advance when making the disc, so that only information playback is possible for playback. The information on the magnetic disk should be played by the player, or like a CD-R, a CD-R disk that can record data only once is used to record data, and the recorded data is provided to the player, using a magneto-optical recording method or a phase change The recording method can record data for repeated read-write discs that have been repeatedly read and written, and can record the recorded data to the player. In these optical recording devices, the recording and playback of data is performed using the light spot where the laser light is focused by the lens on the diffraction limit. The size of this light spot is based on the wavelength of the laser light as λ, and the number of openings of the lens as NA, which is the degree of λ / ΝΑ (Supervised by Kakuda Yoshito, "Basics and Applications of Storage Storage" Institute of Information and Communications, 1995, ρ · 65). (2) (2) 200423109 To record higher density data, that is, to make smaller pit patterns on the optical recording medium, it is necessary to make the light spots smaller. In order to reduce the size of the light spot (ph 〇 t 〇 s ρ 〇 t), the method of shortening the laser light wavelength (λ) by the above formula or the method of increasing the number of lens openings (NA) can be considered. . The wavelengths of semiconductor lasers currently used for optical discs are mainly 780 to 680 nm, orange lasers with shorter wavelengths of 650 nm, and green, blue laser light with short wavelengths are being reviewed. In particular, a blue laser method is proposed in which a wavelength of a light source is about 400 nm, and NA is 0.6 or more 'to obtain a higher recording density. However, due to the short wavelength of the light source or the high NA of the objective lens, the tolerance (tolerance dose) of the disc surface relative to the optical axis from the vertical deviation angle (ti 11 angle) or the thickness of the disc is not uniform. The tolerance will become smaller. The reason why these allowances become smaller is because coma aberrations occur in the case of the tilt angle of the optical disc, and spherical aberrations occur in the case of uneven thickness of the optical disc, which deteriorates the light collection characteristics of the optical head device, and the signal Reading becomes difficult. Conventional compact discs (CDs) can be set on the surface of the recording layer with a thickness of 1.2 mm, while digital multimedia discs (DVD) have a thickness of 0.6 mm. Each disk substrate itself acts as the surface layer. The disk substrate is irradiated with laser light on the recording layer. However, in the method of using a blue laser, in order to increase the number of openings (NA) of the lens and at least make the above-mentioned allowable amount of inclination or the allowable amount of non-uniform thickness of the disc, it is necessary to make the thickness of the surface layer Thin to about 0.1 mm. Therefore, it is impossible to play the role of the surface layer in the substrate itself as in the conventional CD-6-(3) (3) 200423109. The blue laser method is used to form the recording layer (reflection film, recording film, etc.). A laminated film layer is formed on the surface with a thickness of about 0.1 mm, and the laminated film is irradiated with laser light through the coated film layer. However, when a short-wavelength laser such as a blue laser is used, the distance between the optical head and the optical disc is as small as about 0.1 to 0.2 mm. In the optical recording device, in order to achieve a high data transfer rate, it is necessary to rotate the optical disc at a very high speed. With the wavelength of the laser light used, the number of openings (NA) of the lens, the recording capacity of the magnetic disc, and the The combination of desired data transfer rates enables the maximum rotation speed of the disc to be above 2500 rpm, and optionally to be above 5,000 rpm. When the distance between the optical head and the optical disc is as described above, in a very narrow state, rotating the optical disc at such high speeds can make the optical head contact the optical disc, and the film surface layer covering the surface of the recording layer is required to be highly resistant Wearability. In addition, when a shorter-wavelength laser is used, scratches or dust adhesion on the incident surface of the laser light of the optical disc are greatly related to errors during recording and playback. Therefore, in order to prevent such errors in recording and playback, further wear resistance is gradually required on the surface of the thin film that becomes the incident surface of the laser light. As the film surface layer is added with abrasion resistance, it is preferable to have surface lubricity. Although the film surface layer is excellent in abrasion resistance, the surface is poor in lubricity, and the friction force acting on the magnetic disk will definitely increase, while the friction force will also change. At this time, the rotation of the magnetic disk becomes unstable, and recording errors or track errors (t r a c k i n g e r r 〇 r) may occur. (4) 200423109 The surface lubricity imparted to the surface of the film contributes to the improvement of the abrasion resistance of the surface of the film. When the surface of the thin film is imparted with surface lubricity, the added external force is staggered, resulting in an increase in abrasion resistance.

習知有揭示，依照基板，記錄層，保護層，硬塗層之 順序層合之光碟中，該硬塗層爲，含有：膠體二氧化矽微 粒子及有機矽烷化合物之水解生成物予以縮合反應所得有 機被覆二氧化矽（1 )，乙烯性不飽和化合物（2 )，增 滑劑（slip agent )劑（3 )，及光聚合引發劑（4 )， 之組成物之硬化物層的光碟（日本特開2002-245 672號公 報参照）。 但是，增滑劑（3 )所例示之聚矽氧烷油，因與組成 物之其他成分親和性低，故硬化物層之透明性差，或在硬 化物層表面易於滲漏（bleed out )，會有經長期表面潤滑 性無法顯現之問題。It has been conventionally disclosed that in an optical disc laminated in the order of a substrate, a recording layer, a protective layer, and a hard coat layer, the hard coat layer is obtained by subjecting a hydrolyzed product of colloidal silica particles and an organic silane compound to condensation reaction Optical disk (Japan) of a hardened layer of an organic-coated silicon dioxide (1), an ethylenically unsaturated compound (2), a slip agent (3), and a photopolymerization initiator (4) (Reference No. 2002-245 672). However, the polysiloxane oil exemplified by the slip agent (3) has low affinity with other components of the composition, so the transparency of the hardened layer is poor, or the surface of the hardened layer is liable to leak out. There is a problem that the surface lubricity cannot be shown over a long period of time.

一方面，以具有含活性氫官能團與不飽和基之聚矽氧 烷作爲聚合引發劑，則有含使ε-己內酯等內酯予以開環聚 合之以含不飽和基之矽氧烷改質聚酯作爲自由基硬化性成 分之硬化性組成物（参照日本特開2 0 0 1 - 3 3 5 6 2 4號公 報）。但是，該組成物有耐磨損性，透明性差之問題。 本發明之課題，係提供一種光碟，其在磁碟基板之表 面，記錄層及薄膜表層依此順序層合者，使用於資料之記 錄及/或播放之藍色雷射等短波長之雷射光通過薄膜表層 照射於記錄層方式之光碟（以下，簡稱爲光碟）之高性能 化予以實現者。亦即’在該光碟之薄膜表層表面，可顯現 -8 - (5) (5)200423109 耐磨損性，透明性及長期之表面潤滑性之硬塗層所形成之 光碟。 【發明內容】 <發明之揭示> 本發明係提供一種光碟，其在基板面，記錄層與厚度 5〜20 0 // m之薄膜表層，依此順序層合者，使用於資料之 記錄及/或播放之雷射光通過該薄膜表層在照射於該記錄 層方式之光碟中，於該薄膜表層上，形成硬塗層（X)， 該硬塗層（X )係含有，活性能量線硬化性之聚合性單體 (A )，平均粒徑 1〜200 n m之膠體狀二氧化矽 (B )，賦與潤滑性劑（C )，與活性能量線聚合引發劑 (D )，之活性能量線硬化性組成物（Q )之硬化物所成 爲其特徵者。 但是，該聚合性單體（A )，係在含於該硬化性組成 物（Q )之該聚合性單體（A )之總質量中，選自丙烯醯 基及甲基丙烯醯基所成群之聚合性官能團1分子中具有2 個以上多官能性聚合性單體（a · 1 )爲2 0質量％以 上， 該賦與潤滑性劑（C )係含有，1分子中，具有：選 自下述式（1 )所示部分所成部位（c - 1 )與下述式 (2 )〜（5 )所示部分所成群之至少一種所成部位 (c -2 )，與活性能量線硬化性之官能團（c - 3 )，之 賦與潤滑性劑（C - T )。 -9 - (6) (6)200423109 -(S i R 1 R 2 0 ) m- 式（1) (式中，R 2爲1〜8之烷基或苯基之任—攆， m爲1〜1〇〇〇之整數） -R 3 - 式（2 ) -(C Η 2 C Η 2 0 ) X- 式（3) -(CH2CH (CHa) 〇) y- 式（4) -(C ( = 〇）C u Η 2 u 〇 ) t- 式（5 ) (式中，r3爲碳數6〜20之烯烴基’ x及ym5 〜10〇之整數，U爲3〜5之整數，t爲1〜20之擊 數。) 依照本發明係提供一種光碟，其在基板表面，記錄騰 與薄膜表層爲依此順序層合者，使用於資料之記錄及/梁 播放之藍色雷射所代表短波長之雷射光通過薄膜表層照射 於記錄層型式之光碟中，在該薄膜表層之表面’耐磨損性 及長期之表面潤滑性優異，且透明性亦優異之硬塗層的光 碟。 該活性能量線硬化性組成物（Q )，相對於前述聚合 性單體（A ) 1 0 0質量份，以含有前述膠體狀二氧化矽 (B ) 5〜3 0 0質量份，前述賦與潤滑性劑（◦) 0 . 0 1〜1 0質量份，及前述活性能量線聚合引發劑 (D ) 0 · 1〜2 0質量份爲佳。 -10 - (7) (7)200423109 Μ述膠體狀二氧化矽（B )，以具有氫硫基之有機基 g t生$及/或S基’爲鍵結於矽原子之含氫硫基之矽 垸化合物被表面修飾所得修飾膠體狀二氧化矽爲佳。 前述膠體狀二氧化矽（B)，以具有甲基丙烯醯基之 有機基與水解性基及/或羥基爲，鍵結於矽原子之含甲基 丙Μ醯基之矽院化合物被表面修飾所得修飾膠體狀二氧化 矽爲佳。 前述硬塗層（X)之厚度以0.1〜2 0 爲佳。 【實施方式】 <實施發明之最佳型態> 本發明中光碟係’在資料之記錄及/或播放使用短波 長之雷射光，較佳爲波長650 nm之橙色雷射光，更佳爲 更短波長之綠色雷射光或者藍色雷射光之超高密度記錄用 之光碟。亦即，在光碟基板面形成記錄層，進而在該記錄 層之表面形成獨立之薄膜表層，通過該薄膜表層（V)有 雷射光照射之型式之光碟。 本發明之光碟係，在上述構成之光碟薄膜表層之表 面，進而形成活性能量線硬化性組成物（Q )之硬化物所 成硬塗層（X )。 在活性能量線硬化性組成物（Q )(以下，簡稱爲組 成物（Q ))中，活性能量線硬化性之聚合性單體（A ) (以下，稱爲聚合性單體（A ))，係在後述之活性能量 線聚合引發劑（D )之存在下，照射活性能量線，而可開 始聚合反應之單體。具體而言，係將作爲聚合性官能團 -11 - (8) (8)200423109 之’ 1分子中具有2個以上丙烯醯基或甲基丙烯醯基之多 官能性聚合性單體（a · 1 )(以下，稱爲單體（a -1))，與後述之單官能性聚合性單體（a - 2 )所代表 之其他聚合性單體予以總括的表示。但是，並不含有該當 於後述之賦與潤滑性劑（C )化合物。在以下之説明中， 丙烯醯基及甲基丙烯醯基總稱爲甲基丙烯醯基。 在聚合性單體（A )中，單體（a - 1 )則相當於日 本特開平1 0- 8 1 8 3 9號公報段落號碼0013〜00 5 2所記載之 多官能性化合物（a )。亦即，作爲可藉由活性能量線聚 合之聚合性官能團，係1分子中具有2個以上甲基丙烯醯 基之多官能性聚合性單體。 在本發明中之單體（a · 1 )方面，就顯現高度耐磨 損性之觀點而言，以分子中具有3個以上聚合性官能團， 每一官能團之分子量爲1 20以下者爲佳。在滿足此等條件 之單體（a - 1 )方面，則有以下之化合物。 爲新戊四醇或聚新戊四醇，與甲基丙烯酸之反應生成 物的聚酯，且甲基丙烯醯基爲3個以上，較佳爲4〜20個 之多官能性化合物。具體而言，以三羥甲基丙烷三甲基丙 烯酸酯，新戊四醇三甲基丙烯酸酯，新戊四醇四甲基丙烯 酸酯，二新戊四醇六甲基丙烯酸酯等爲佳。 一方面’在分子内具有烏拉坦（urethane)鍵結之含 甲基丙烯醯基之化合物（以下，稱爲丙烯基烏拉坦），其 烏拉坦鍵結係其氫鍵結之作用作爲擬似交聯點來作用，每 一官能團之分子量即使不會比上述爲小，亦可顯現充分高 -12- (9) (9)200423109 度的耐磨損性，而可恰當的使用。在滿足此等條件之單體 (a - 1 )方面，則以以下之化合物爲佳。 爲新戊四醇或聚新戊四醇，聚異氰酸酯，與羥基烷基 甲基丙烯酸酯之反應生成物的丙烯基烏拉坦，且甲基丙烯 醯基爲3個以上，較佳爲4〜2 0個之多官能性化合物。 新戊四醇或聚新戊四醇之含羥基聚甲基丙烯酸酯與聚 異氰酸酯之反應生成物的丙烯基烏拉坦，且甲基丙烯醯基 有3個以上，較佳爲具有4〜2 0個之多官能性化合物。 組成物（Q )，作爲聚合性單體（A )，可含有單體 (a - 1 )以外之聚合性單體。在單體（a - 1 )以外之聚合性 單體（A)方面，在1分子中具有1個甲基丙烯醯基之單 官能性聚合性單體（以下，稱爲單體（a - 2 ))或甲基 丙烯醯基以外之聚合性官能團1個以上之化合物。但是， 甲基丙烯醯基以外之聚合性官能團，因活性能量線所致硬 化性並非充分之情況相當多，又獲得亦非容易，因此單體 (a - 1 )以外之聚合性單體（a )方面以單體（a - 2 ) 爲佳。 在單體（a-2 )方面，一般式CH2 = C (R4) COOC 2 H 2z+i(R4爲氫原子或甲基，ζ 爲·1〜13之整數。C ZH2 爲直鏈構造或分支構造均 可。）所示之烷基甲基丙烯酸酯，烯丙基甲基丙烯酸酯， 苄基甲基丙烯酸酯，丁氧基乙基甲基丙烯酸酯，丁二醇甲 基丙烯酸酯，丁氧基三乙二醇單甲基丙烯酸酯，第三丁基 胺乙基甲基丙烯酸酯，3 ·氯-2 -羥基丙基甲基丙烯酸 -13- (10) 200423109On the one hand, using polysiloxanes containing active hydrogen functional groups and unsaturated groups as polymerization initiators, Hardening composition of high-quality polyester as a radical hardening component (see Japanese Patent Laid-Open Nos. 2000-1-3 3 5 6 2 4). However, this composition has problems of abrasion resistance and poor transparency. The subject of the present invention is to provide an optical disc, in which a recording layer and a thin film surface layer are laminated in this order on the surface of a magnetic disk substrate, and used for short-wavelength laser light such as blue laser for data recording and / or playback. High-performance optical discs (hereinafter, simply referred to as optical discs) irradiated with a recording layer method through a thin film surface layer are realized. That is, a disc formed by a hard coating layer on the surface of the film surface of the disc. -8-(5) (5) 200423109 Wear resistance, transparency and long-term surface lubricity. [Summary of the invention] < Disclosure of the invention > The present invention provides an optical disc having a recording layer on a substrate surface and a thin film surface layer having a thickness of 5 to 20 0 // m, and those laminated in this order are used for data recording. And / or played laser light passes through the surface layer of the film and is irradiated on the disc with the recording layer method, and a hard coating layer (X) is formed on the surface layer of the film. Polymerizable monomer (A), colloidal silicon dioxide (B) with an average particle diameter of 1 to 200 nm, imparting a lubricating agent (C), and active energy ray polymerization initiator (D), the active energy The hardened material of the linear hardening composition (Q) is characterized by it. However, the polymerizable monomer (A) is selected from the group consisting of acrylfluorenyl group and methacrylfluorenyl group in the total mass of the polymerizable monomer (A) contained in the curable composition (Q). The polymerizable functional group of the group has two or more polyfunctional polymerizable monomers (a · 1) in an amount of 20% by mass or more. The lubricating agent (C) is contained in one molecule. And the active energy from the site (c-1) formed by the part represented by the following formula (1) and at least one site (c-2) formed by the group represented by the following formulas (2) to (5) Linear hardenable functional group (c-3), and lubricating agent (C-T). -9-(6) (6) 200423109-(S i R 1 R 2 0) m- formula (1) (where R 2 is any of 1 to 8 alkyl or phenyl groups-撵, m is 1 Integer to 100%) -R 3-Formula (2)-(C Η 2 C Η 2 0) X- Formula (3)-(CH2CH (CHa) 〇) y- Formula (4)-(C ( = 〇) C u Η 2 u 〇) t- formula (5) (where, r3 is an olefin group of 6 to 20 carbons' x and ym5 to 100 integers, U is an integer of 3 to 5 and t is The number of hits is from 1 to 20.) According to the present invention, an optical disc is provided. On the surface of the substrate, the recording layer and the film surface layer are laminated in this order, which is represented by the blue laser used for data recording and / or beam playback. A short-wavelength laser light is irradiated to the recording layer type disc through the surface layer of the film, and the surface of the surface layer of the film is a hard-coated disc having excellent abrasion resistance and long-term surface lubricity, and excellent transparency. This active energy ray-curable composition (Q) contains 5 to 300 parts by mass of the colloidal silicon dioxide (B) in an amount of 100 to 100 parts by mass with respect to the polymerizable monomer (A). The lubricating agent (◦) is preferably 0.01 to 10 parts by mass, and the active energy ray polymerization initiator (D) is preferably 0 to 1 to 20 parts by mass. -10-(7) (7) 200423109 The colloidal silicon dioxide (B) described above is a hydrogen-sulfur group containing a hydrogen-sulfur-containing organic group and / or an S group as a bond to a silicon atom. The modified colloidal silicon dioxide obtained by the surface modification of the silicon hafnium compound is preferred. The colloidal silicon dioxide (B) is an organic group having a methacryl group and a hydrolyzable group and / or a hydroxyl group, and a silicon compound containing a methyl propyl group which is bonded to a silicon atom is surface-modified The resulting modified colloidal silica is preferred. The thickness of the hard coat layer (X) is preferably 0.1 to 20. [Embodiment] < The best mode for implementing the invention > In the present invention, the optical disc system uses a short-wavelength laser light for data recording and / or playback, preferably an orange laser light with a wavelength of 650 nm, and more preferably Discs for ultra-high density recording of shorter wavelength green laser light or blue laser light. That is, a recording layer is formed on the substrate surface of the optical disc, and then an independent thin film surface layer is formed on the surface of the recording layer. The thin film surface layer (V) is a type of optical disc irradiated with laser light. In the optical disc system of the present invention, a hard coat layer (X) is formed on the surface of the surface of the optical disc film having the above-mentioned structure, and a hardened body of the active energy ray-curable composition (Q) is formed. In the active energy ray-curable composition (Q) (hereinafter, simply referred to as the composition (Q)), the active energy ray-curable polymerizable monomer (A) (hereinafter, referred to as the polymerizable monomer (A)) In the presence of an active energy ray polymerization initiator (D) described later, the monomer is a monomer that can irradiate an active energy ray and start a polymerization reaction. Specifically, it is a polyfunctional polymerizable monomer having a polymerizable functional group of 11-(8) (8) 200423109 as a polyfunctional polymerizable monomer having two or more acrylfluorenyl groups or methacrylfluorenyl groups (a · 1 ) (Hereinafter, referred to as monomer (a-1)), and other polymerizable monomers represented by the monofunctional polymerizable monomer (a-2) described below are collectively represented. However, it does not contain the lubricating agent (C) compound to be described later. In the following description, acrylfluorenyl and methacrylfluorenyl are collectively referred to as methacrylfluorenyl. In the polymerizable monomer (A), the monomer (a-1) corresponds to the polyfunctional compound (a) described in Japanese Patent Application Laid-Open No. 10- 8 1 8 3 9 paragraph number 0013 to 00 5 2 . That is, the polymerizable functional group that can be polymerized by active energy rays is a polyfunctional polymerizable monomer having two or more methacrylfluorene groups in one molecule. In terms of the monomer (a · 1) in the present invention, from the viewpoint of exhibiting high abrasion resistance, it is preferable that the molecule has three or more polymerizable functional groups, and the molecular weight of each functional group is 1 to 20. As for the monomer (a-1) satisfying these conditions, there are the following compounds. A polyfunctional compound consisting of neopentyl tetraol or polypentaerythritol, a reaction product of methacrylic acid, and three or more methacryl groups, preferably four to twenty. Specifically, trimethylolpropane trimethylacrylate, neopentaerythritol trimethacrylate, neopentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate and the like are preferred. On the one hand, a methacrylfluorenyl-containing compound (hereinafter referred to as propenyl urethane) having a urethane bond in the molecule, and its uranium bond is related to its hydrogen bonding as a pseudo-crosslinking. From the point of view, even if the molecular weight of each functional group is not smaller than the above, it can show sufficiently high abrasion resistance of -12- (9) (9) 200423109 degrees, and can be used appropriately. In terms of the monomers (a-1) satisfying these conditions, the following compounds are preferred. It is neopentaerythritol or polypentaerythritol, polyisocyanate, and propylene urethane formed by the reaction of hydroxyalkyl methacrylate, and the number of methacryl groups is 3 or more, preferably 4 to 2. 0 polyfunctional compounds. Propyl urethane, a reaction product of hydroxyl-containing polymethacrylate and polyisocyanate of neopentyl tetraol or polypentaerythritol, and more than 3 methacrylfluorene groups, preferably 4 to 2 0 A multifunctional compound. The composition (Q) may contain a polymerizable monomer other than the monomer (a-1) as the polymerizable monomer (A). As for the polymerizable monomer (A) other than the monomer (a-1), a monofunctional polymerizable monomer (hereinafter, referred to as a monomer (a-2) having one methacrylfluorene group in one molecule )) Or a compound having one or more polymerizable functional groups other than a methacryl group. However, there are many cases where polymerizable functional groups other than methacrylfluorene are not sufficiently hardened by active energy rays, and it is not easy to obtain them. Therefore, polymerizable monomers (a-1) other than monomers (a-1) In terms of), monomer (a-2) is preferred. In terms of monomer (a-2), the general formula CH2 = C (R4) COOC 2 H 2z + i (R4 is a hydrogen atom or a methyl group, and ζ is an integer of 1 to 13. C ZH2 is a linear structure or branch The structure is acceptable.) The alkyl methacrylate, allyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butanediol methacrylate, butoxy Triethylene glycol monomethacrylate, tertiary butylamine ethyl methacrylate, 3-chloro-2-hydroxypropylmethacrylate-13- (10) 200423109

酯，氰基乙基甲基丙燦酸酯，環己基甲基丙燃酸酯 2,3 -二溴丙基甲基丙烯酸酯，二環戊烯基甲基丙烯酸酯， Ν，Ν-二乙基胺乙基甲基丙烯酸酯，Ν，Ν-二甲基胺乙基甲 基丙烯酸酯，2 -乙氧基乙基甲基丙烯酸酯，2 - ( 2 -乙氧 基乙氧基）乙基甲基丙烯酸酯，2 -乙基己基甲基丙烯酸 酯，甘油醯基（glyceroyl)甲基丙烯酸酯，環氧丙基甲基 丙烯酸酯，十七基氟癸基甲基丙烯酸酯，2-羥基乙基甲 基丙烯酸酯，2-羥基-3 -甲基丙烯醯基氧丙基三甲銨氯 化物，2-羥基丙基甲基丙烯酸酯，甲基丙烯基氧丙基 三甲氧基矽烷，2 -甲氧基乙基甲基丙烯酸酯，甲氧基二 乙二醇甲基丙烯酸酯，甲氧基三乙二醇甲基丙烯酸酯，甲 氧基四乙二醇甲基丙烯酸酯，甲氧基二丙二醇甲基丙烯酸 酯，甲氧基化環十三碳烯（decatriene )甲基丙烯酸酯， 嗎福林甲基丙嫌酸醋，壬基苯氧基聚乙二醇甲基丙稀酸 酯’壬基苯氧基聚丙二醇甲基丙烯酸酯，八氟戊基甲基丙 烯酸酯’苯氧基羥基丙基甲基丙烯酸酯，苯氧基乙基甲基 丙烯酸酯，苯氧基二乙二醇甲基丙烯酸酯，苯氧基四乙二 醇甲基丙烯酸酯’苯氧基六乙二醇甲基丙烯酸酯，苯氧基 甲基丙烯酸酯，聚丙二醇甲基丙烯酸酯，2-磺酸鈉乙氧 基甲基丙烯酸酯’四氟丙基甲基丙烯酸酯，四氫糠基 (furfuryl )甲基丙烯酸酯，三氟乙基甲基丙烯酸酯，乙 烯乙酸酯，N -乙烯己內醯胺，N -乙烯呲咯啶酮，二環戊 二烯基甲基丙烯酸酯，異冰片基丙烯酸酯等。 在組成物（Q )中’於聚合性單體（A )之總質量 -14- (11) 200423109 中，20〜100質量％爲單體（a、，以5〇〜 100質量％爲佳，70〜1 0 0質量％更佳。組成Ester, cyanoethylmethylpropionate, cyclohexylmethylpropionate 2,3-dibromopropylmethacrylate, dicyclopentenylmethacrylate, Ν, Ν-diethyl Methylamine ethyl methacrylate, N, N-dimethylamine ethyl methacrylate, 2-ethoxyethyl methacrylate, 2- (2-ethoxyethoxy) ethyl Methacrylate, 2-Ethylhexyl Methacrylate, Glyceroyl Methacrylate, Glycidyl Methacrylate, Heptafluorofluorodecyl Methacrylate, 2-Hydroxyethyl Methyl methacrylate, 2-hydroxy-3 -methacrylfluorenyloxypropyltrimethylammonium chloride, 2-hydroxypropylmethacrylate, methacryloxypropyltrimethoxysilane, 2-methyl Oxyethyl methacrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, methoxydipropylene glycol Methacrylate, methoxylated decatriene methacrylate, morpholin methyl propionate, nonylphenoxy polyethylene glycol Acrylic acid esters 'nonylphenoxy polypropylene glycol methacrylate, octafluoropentyl methacrylate' phenoxyhydroxypropyl methacrylate, phenoxyethyl methacrylate, phenoxy Diethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate 'phenoxyhexaethylene glycol methacrylate, phenoxy methacrylate, polypropylene glycol methacrylate, 2 -Sodium sulfonate ethoxy methacrylate 'tetrafluoropropyl methacrylate, tetrafurfuryl methacrylate, trifluoroethyl methacrylate, ethylene acetate, N-ethylene Caprolactam, N-vinylpyrrolidone, dicyclopentadienyl methacrylate, isobornyl acrylate and the like. In the composition (Q), in the total mass of the polymerizable monomer (A) -14- (11) 200423109, 20 to 100% by mass is the monomer (a, preferably 50 to 100% by mass, 70 to 100% by mass is more preferable. Composition

物（Q)所含聚合性單體（A)之中，單體（a _ 1 )之比 例在此範圍內時，組成物（Q )之硬化物所成硬塗層 (X )(以下’單稱爲硬塗層（X ))之耐磨損性特別優 異。在組成物（Q )中，膠體狀二氧化砍（B )，在分散 媒中分散成膠體狀之矽酸酐之超微粒孓，分散媒並無特別 限疋’通常可使用水；甲醇’乙醇’轉丙醇，正丁醇，乙 二醇般之低級醇類；甲溶纖劑’乙基溶纖劑，丁基溶纖 劑，丙二醇單甲醚乙酸酯等溶纖劑賴；二甲乙艦胺，甲 苯，二甲苯，乙酸甲酯，乙酸乙酯，乙酸戊酯，丙酮等。 膠體狀二氧化矽（B )之平均粒悝爲1〜2 〇 〇 n m，爲顯現硬塗層（X )之局度透明性，特佳爲平均粒 徑1〜5 0 n m。Among the polymerizable monomers (A) contained in the substance (Q), when the proportion of the monomer (a _ 1) is within this range, the hard coat (X) (hereinafter ' The hard coating (X) is particularly excellent in abrasion resistance. In the composition (Q), colloidal dioxide (B) is dispersed into a colloidal ultrafine particle of silicic anhydride in a dispersing medium. The dispersing medium is not particularly limited. 'Usually water can be used; methanol' ethanol ' Transpropanol, n-butanol, ethylene glycol-like lower alcohols; A cellosolve 'ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether acetate, and other cellosolvents; dimethyl ethyl amine, Toluene, xylene, methyl acetate, ethyl acetate, amyl acetate, acetone and the like. The average particle size of the colloidal silicon dioxide (B) is 1 to 2000 nm. In order to show the local transparency of the hard coat layer (X), an average particle diameter of 1 to 50 nm is particularly preferred.

又膠體狀一氧化砂（B )爲提局其分散穩定性，可使 用粒子表面以水解性矽院化合物之水解物所修飾者。在此 所謂「以水解物使表面被修飾」，係在膠體狀二氧化矽粒 子表面之一部份或全部砂院醇基，使政院化合物之水解物 鍵結爲物理的或化學的之狀態，藉此可使表面特性改質。 又，水解物之縮合反應所進行者亦含有相同鍵結之二氧化 矽粒子。此表面修飾係在二氧化矽粒子存在下，使矽烷化 合物之水解性基之一部份或全部水解，或使水解與縮合反 應產生者更容易進行。 在水解性矽烷化合物方面，以具有甲基丙烯醯基，胺 -15- (12) (12)200423109 基’環氧基’氫硫基等官能性基之有機基，與烷氧基等水 解性基及/或羥基’爲鍵結於矽原子之矽烷化合物爲佳。 在本說明書中所謂水解性基，係指在與矽原子之鍵結部分 可水解之基。例如，有3 -甲基丙烯醯基氧丙基三甲氧基 石夕院’ 2 -甲基丙烯醯基氧乙基三甲氧基矽烷，3 -甲基丙 燃醒基氧丙基三乙氧基矽烷，2 -甲基丙烯醯基氧乙基三 乙氧基基砂烷’ 3 -胺丙基三乙氧基矽烷，3 -胺丙基三甲 氧基砂垸’ N-( 2-胺乙基）-3-胺丙基甲基二甲氧基矽 烷，3-環氧丙氧基丙基三甲氧基矽烷，3-氫硫丙基三甲 氧基砂院等爲佳。 在水解性矽烷化合物方面，具有氫硫基之有機基與水 解性基及/或羥基爲鍵結於矽原子之含氫硫基之矽烷化合 物，就與聚合性單體（A )之反應性高而言爲佳。在含氫 硫基之矽烷化合物方面，具體而言有下述式（6 )所示之 化合物例示。In addition, colloidal sand oxide (B) is used to improve the dispersion stability of the particles, and the surface of the particles can be modified with a hydrolyzate of a hydrolyzable silicon compound. The so-called "surface modification with hydrolysate" here refers to a part or all of the alcohol compound on the surface of colloidal silica particles, so that the hydrolysate of the compound of the government compound is bonded to a physical or chemical state. , Which can improve the surface characteristics. In addition, the condensation reaction of the hydrolysate proceeds with silica particles having the same bond. This surface modification is to partially or fully hydrolyze a hydrolyzable group of a silane compound in the presence of silica particles, or to make it easier for the producer of the hydrolysis and condensation reaction. In terms of hydrolyzable silane compounds, organic groups having functional groups such as a methacryl group, an amine-15- (12) (12) 200423109 group, an 'epoxy group', a hydrogen thio group, and a hydrolyzable group such as an alkoxy group A silane compound having a group and / or a hydroxyl group is preferably a silicon atom. The term "hydrolyzable group" as used in this specification refers to a group that is hydrolyzable in a bonding portion with a silicon atom. For example, there are 3-Methacrylamidooxypropyltrimethoxy silanes' 2-Methacrylamidooxyethyltrimethoxysilane, 3-Methylpropanyloxypropyltriethoxysilane , 2-Methacrylamidooxyethyltriethoxysarane '3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysarane' N- (2-aminoethyl) 3-Aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-hydrothiopropyltrimethoxysilane, etc. are preferred. In terms of hydrolyzable silane compounds, an organic group having a hydrogen sulfide group and a hydrolyzable group and / or a hydroxyl group are bonded to a silicon atom and a hydrogen sulfide group-containing silane compound is highly reactive with the polymerizable monomer (A) It's better. Specific examples of the hydrogen-thio group-containing silane compound include a compound represented by the following formula (6).

HS-R-SiXLR03-L 式（6) (式中，R表示烯烴基，R°表示烷基，X表示經基 或水解性基，L表示1〜3之整數。） 上述式中’ R較佳爲碳數2〜6 (最佳爲3 )之烯烴 基，R°較佳爲碳數4以下之院基’尤其是以甲基與乙基 爲佳。X爲水解性基爲佳’尤其是碳數4以下之烷氧基爲 佳。在此院氧基方面進而以甲氧基與乙氧基水解性良好較 -16- (13) 200423109 恰當。L以2〜3爲佳。 上述式所示含氫硫S t 5夕i：完化;€物之ft $ W如! Μ T 0 例示。又，Me表示甲基’ Ε 1表示乙基’ Ργ表示正丙 基。 Η S - C Η 2 C Η 2 C Η 2 -S i ( 〇： Me )3， Η S -C Η 2 C Η 2 C Η 2 - s 1 ( 〇 E t :) 3 1 Η S -C Η 2 C Η 2 C Η 2 - s (〇 P r )3 Η S -C Η 2 C Η 2 C Η 2 - s i Me (OM e )2 ， Η S -C Η 2 C Η 2 C Η 2 - s Me (〇 E t )、 Η S -C Η 2 C Η 2 C Η 2 - S i .M e (〇 P r )2 Η S -C Η 2 C Η 2 C Η 2 祕 S i Me 2 (( )M e ) Η S • C Η 2 C Η 2 C Η 2 - S i Me 2 (〇E t ) Η S -C Η 2 C Η 2 C Η 2 - s i M e 2 ( 〇P r ) Η S -C Η 2 C Η 2 C Η 2 - s i C 1 ： 3 , Η S -C Η 2 C Η 2 C Η 2 - s i B r 3 J Η S -C Η 2 C Η 2 C Η 2 - s i Me c 1 2， Η S -C Η 2 C Η 2 C Η 2 - s i M e B r 2 丨》 Η S -C Η 2 C Η 2 C Η 2 -s i Me 2 ) C 1 > Η S • C Η 2 C Η 2 C Η 2 _ s i M e 2 B : Γ 0HS-R-SiXLR03-L Formula (6) (In the formula, R represents an olefin group, R ° represents an alkyl group, X represents a vial group or a hydrolyzable group, and L represents an integer of 1 to 3.) In the above formula, R is larger than It is preferably an olefin group having 2 to 6 carbon atoms (preferably 3), and R ° is preferably a group having 4 carbon atoms or less. Especially preferred are methyl and ethyl groups. X is preferably a hydrolyzable group ', especially an alkoxy group having 4 or less carbon atoms. In this respect, methoxy and ethoxy are better hydrolyzed than -16- (13) 200423109. L is preferably 2 to 3. The above formula shows hydrogen-containing sulfur S t 5 xi: finished; ft $ W of the material is like! Μ T 0 is exemplified. In addition, Me represents methyl 'E 1 represents ethyl' and Pγ represents n-propyl. Η S-C Η 2 C Η 2 C Η 2 -S i (〇: Me) 3, Η S -C Η 2 C Η 2 C Η 2-s 1 (〇E t :) 3 1 Η S -C Η 2 C Η 2 C Η 2-s (〇P r) 3 Η S -C Η 2 C Η 2 C Η 2-si Me (OM e) 2, Η S -C Η 2 C Η 2 C Η 2-s Me (〇E t), Η S -C Η 2 C Η 2 C Η 2-S i .M e (〇P r) 2 Η S -C Η 2 C Η 2 C Η 2 Se Me 2 (( ) M e) Η S • C Η 2 C Η 2 C Η 2-S i Me 2 (〇E t) Η S -C Η 2 C Η 2 C Η 2-si M e 2 (〇P r) Η S -C Η 2 C Η 2 C Η 2-si C 1: 3, Η S -C Η 2 C Η 2 C Η 2-si B r 3 J Η S -C Η 2 C Η 2 C Η 2-si Me c 1 2, Η S -C Η 2 C Η 2 C Η 2-si M e B r 2 丨》 Η S -C Η 2 C Η 2 C Η 2 -si Me 2) C 1 > Η S • C Η 2 C Η 2 C Η 2 _ si M e 2 B: Γ 0

又，在水解性砂垸化合物 有機基與水解性基及/或許基 基丙烯醯基矽烷化合物 」，就與 方面，具有甲基丙烯醯基之 ，爲鍵結於矽原子之含有甲 聚合性單體（A )之反應性 -17- (14)200423109 高及其 烷化合 佳。 C Η 2 ( R 0表 整數。 上 基，R 佳。X 佳。在 佳。L 上 例係以 C (OM e -S i C Η 2 C Η 2 (R 5 C Η 2 鍵結之定性而言較佳。在含有甲基丙烯醯基之矽 物方面’具體而言以下述式（7 )所示之化合物爲 -C (R5) COO-R.g ix lR〇3.l 式（7) 式中，R5表示氫原子或甲基，R表示烯烴基， 示烷基，X表示羥基或水解性基，L表示1〜3之 ) 述式中，R較佳爲碳數2〜6 (最佳爲3 )之烯烴 較佳爲碳數4以下之院基，尤其是甲基與乙基爲 以水解性基爲佳，尤其是碳數4以下之烷氧基爲 此烷氧基方面進而以甲氧基與乙氧基水解性良好較 以2〜3爲佳。 述式所示之含有甲基丙烯醯基之矽烷化合物之代表 下所例示。In addition, in the hydrolyzable sand compound, the organic group and the hydrolyzable group and / or the methacrylic acid fluorenyl silane compound ", and the methacryl methionyl group is a polymerizable monomer containing a methyl group bonded to a silicon atom. The reactivity of the compound (A) is 17- (14) 200423109 and its alkylation is good. C Η 2 (R 0 represents an integer. Upper base, R is good. X is good. In good. L The above example is based on the qualitative character of C (OM e -S i C Η 2 C Η 2 (R 5 C Η 2 In terms of a methacrylfluorenyl group-containing silicon compound, specifically, the compound represented by the following formula (7) is -C (R5) COO-Rg ix lR〇3.l Formula (7) R5 represents a hydrogen atom or a methyl group, R represents an alkene group, an alkyl group, X represents a hydroxyl group or a hydrolyzable group, and L represents 1 to 3) In the above formula, R is preferably a carbon number of 2 to 6 (most preferably 3) The olefin is preferably a group having a carbon number of 4 or less, and especially a methyl group and an ethyl group are preferably a hydrolyzable group, especially an alkoxy group having a carbon number of 4 or less is an alkoxy group and further a methoxy group The group and the ethoxy group have better hydrolyzability than 2 to 3. The methacryl group-containing silane compound represented by the formula is representatively exemplified below.

Η 2 = C ( R 5 ) COO- C Η 2 C Η 2 C Η 2 - S i )3，C Η 2 = C ( R 5 ) -COO- C H 2 C H 2 C H 2 (〇E t ) a » CH2 =C (R 5 ) COO- C H 2 C H 2 -Si(〇Pr)3，CH2=C(R5) c〇0-C H 2 C H 2 - S i M e (OM e ) 2，c H 2 = C )COO-C H2CH2 C H 2 - S i M e (〇 £ t ) <>， = C(R5)COO-CH2 C H 2 C H 2 . ς i m p -18- 200423109Η 2 = C (R 5) COO- C Η 2 C Η 2 C Η 2-S i) 3, C Η 2 = C (R 5) -COO- CH 2 CH 2 CH 2 (〇E t) a » CH2 = C (R 5) COO- CH 2 CH 2 -Si (〇Pr) 3, CH2 = C (R5) c〇-CH 2 CH 2-S i M e (OM e) 2, c H 2 = C) COO-C H2CH2 CH 2-S i M e (〇 £ t) < >, = C (R5) COO-CH2 CH 2 CH 2. Σ imp -18- 200423109

( 〇 Ρ r ) 2 c H 2 = C (R 5 ) coo- c H 2 C H 2 C Η 2 -S i M e 2 (〇 M e ) 1 c H 2 = c (R5 )COO- ch2 C Η 2 C ： H ： 2 - s i M e 2 ( 0 E t )， c H 2 C ( R 5 ) COO -C H 2 C H 2 C H 2 * s i M e 2 ( 〇 Ρ r ) 1 C H 2 =c ( R 5 )COO- c H 2 C H 2 C Η 2 -S i C 1 ； 3 ， c H ： 2 = c ( R 5 ) COO- C H 2 C Η 2 C H 2 -S i B r 3 ， CH 2 =C ( ；R i 5 )丨 coo- C Η 2 C H 2 C H 2 - S i M e C 1 2 1 C H 2 == C ( R 5 ) COO -C H 2 C H 2 C H 2 - s i M e B Γ 2， C Η 2 - =C ( R 5 ) COO -C H 2 c H 2 c H 2 一 S i Μ e 2 C 1 ， C H 2 = c ( R 5 1 ) COO- C H 2 C Η 2 C H 2 -S i Me 2 B i O(〇Ρ r) 2 c H 2 = C (R 5) coo- c H 2 CH 2 C Η 2 -S i M e 2 (〇M e) 1 c H 2 = c (R5) COO- ch2 C Η 2 C: H: 2-si M e 2 (0 E t), c H 2 C (R 5) COO -CH 2 CH 2 CH 2 * si M e 2 (〇ρ r) 1 CH 2 = c (R 5) COO- c H 2 CH 2 C Η 2 -S i C 1; 3, c H: 2 = c (R 5) COO- CH 2 C Η 2 CH 2 -S i B r 3, CH 2 = C (; R i 5) 丨 coo- C Η 2 CH 2 CH 2-S i M e C 1 2 1 CH 2 == C (R 5) COO -CH 2 CH 2 CH 2-si M e B Γ 2, C Η 2-= C (R 5) COO -CH 2 c H 2 c H 2 -S i Μ e 2 C 1, CH 2 = c (R 5 1) COO- CH 2 C Η 2 CH 2 -S i Me 2 B i O

在前述組成物（Q )中，聚合性單體（A )與膠體狀 二氧化矽（B )之比例並無特別限定，相對於聚合性單體 (A ) 1 0 0質量份，膠體狀二氧化矽（B )(固形成 分）以含有5〜300質量份爲佳，以含有1 〇〜2 0 0 質量份更佳。膠體狀二氧化矽（B )之比例在上述範圍 時，所形成之硬塗層（X )，在耐磨損性，透明性及施加 外力之際之機械的強度中優異。膠體狀二氧化矽（B)之 比例在不滿5質量份時，硬塗層（X )有耐磨損性差之傾 向。一方面，膠體狀二氧化矽（B )之比例超過3 0 0質 量份時，在硬塗層（X)易產生霧度，且，光碟受外力被 強制變形之際，在硬塗層（X )易於產生龜裂等。 -19- (16) (16)200423109 在過成物（Q )中，賦與潤滑性劑（c )，係總括地 表示以下説明之賦與潤滑性劑（C - τ )與後述之其他賦 與潤滑性劑。 在組成物（Q )中’聚合性單體（A )與賦與潤滑性 劑（C )之比例並無特別限定，相對於聚合性單體（A ) 1 0 0質量份，賦與潤滑性劑（C )以〇 · 〇 1〜1 〇質 星份爲佳，以0 . 1〜5 · 0質量份更佳。賦與潤滑性劑 (C )之比例在上述之範圍時，所形成之硬塗層（圖χ ) 之表面潤滑性及耐磨損性優異。賦與潤滑性劑（C )在未 滿0 . 0 1質量份時’硬塗層（X )會有表面潤滑性差之 傾向。一方面，賦與潤滑性劑（c )超過1 0質量份時， 硬塗層（X )自體可被可塑化，耐磨損性會有降低之傾 向。 在組成物（Q )中賦與潤滑性劑（C - T )，係選自 式（1 )所示之部分所成部位（c - 1 )，式（2 )〜 (5 )所示部分所成群之至少一種所成部位（c - 2 )及 活性能量線硬化性之官能團（c - 3 )，在1分子中兼有 之化合物。 -(S i R 1 R 2 0 ) m- (1) (式中，R 2爲碳數1〜8之烷基，苯基之任一 種，m爲1〜1000之整數。） -20- (17)200423109 R3- 式（2 ) 式（3 ) 式（4 ) 式（5 ) C H 2CH20 ) x-CH2CH(CH3)0) C (=0) C u H 2 u 0 ) t- (上述式中，R3爲碳數6〜2 0之烯烴基，乂及丫 爲5〜10〇之整數，U爲3〜5之整數，七爲丄〜20 之整數。） 賦與潤滑性劑（C - T )，具有上述式（1 )所示部 分所成之部位（c - 1 )(以下，單稱爲部位（^ · 1 ) ° )，使得所形成之硬塗層（X )表面潤滑性優異。 具體而言，如後所示之順序，在測定硬塗膜（X )層表面 8力摩擦係數之際，耐摺動性試驗前後之動摩擦係數均爲 〇 · 1以下。 上述式（1)中，R 2，在每一矽氧烷單位可爲 相同或相異。在該當於上述式（1 )之部分方面，具體而 口例如，聚二甲基聚矽氧烷單元，聚甲基苯基聚矽氧烷單 元’聚二苯基聚矽氧烷單元等。顯示聚合度之㈤係丄〜 1 0 0 0之整數，較佳爲1〜5 0 0之整數。m在該範圍 時’硬塗層（X )之表面潤滑性優異。m超過1 0 0 0時 粘度會過高，與組成物（Q )之其他成分難以混合。 在組成物（Q )中’賦與潤滑性劑（C -T )在式 (1 )所示之部分所成部位（c - 1 )中，以不同形式被 特定之部位，可在同一分子内有2種以上。 -21 - (18) (18)200423109 又’組成物（Q )，在賦與潤滑性劑（c - τ )方 面，可倂用多種以具有不同形式所特定之部位（c - 1 ) 之賦與潤滑性劑（c - T )。 選自賦與潤滑性劑（c - T )之式（2 )〜（5 )所 示部分所成群之至少一種之部位（c - 2 )(以下，稱爲 「部位（c - 2 )」° ) ’具有表現與聚合性單體（a ) 之相溶性之機能。 賦與潤滑性劑（c - T )之部位（c - 1 )，因與聚合 性單體（A )所形成之樹脂基質之親和性低，故在硬化組 成物（Q )之際，容易滲漏於樹脂基質之表面，而有損及 硬化後硬塗層（X )之透明性之傾向。 賦與潤滑性劑（C - τ )，其部位（c - 2 )因與聚合 性單體（A )之相溶性優異，儘管有與聚合性單體（a ) 之親和性低之部位（c - 1 )，但相對於聚合性單體 (A )亦具有適度相溶性。 在組成物（Q ) ’賦與潤滑性劑（C - T )相對於聚 合性單體（A )因具有適度相溶性，故使組成物（Q )塗 布於薄膜表層之表面之際，在不會損及硬化前塗膜之透明 性下，賦與潤滑性劑（C · T )則在塗膜表面偏析。因此 並不會損及硬化後之硬塗層（X )之透明性。 上述式（2)所示之部分，碳數爲具有6〜2 0之直 鏈或分支之烯烴基。碳數在該範圍內時，賦與潤滑性劑 (C · T )相對於聚合性單體（a )之相溶性爲適度，且 該基之結晶性並非過強，故硬塗層（X )表面潤滑性及透 -22- (19) 200423109 明性優異。碳數在5以下時，相對於聚合性單體（A )之 相溶性低，會損及硬化前塗膜之透明性。此係會損及硬化 後硬塗層（X )之透明性。一方面，碳數超過2 0時，該 基之結晶性因會增強，還是會損及硬塗層（X )之透明 性。 上述式（3 )所示之部分，表示環氧乙烷之單元。顯 示聚合度之X爲5〜1 00之整數。X在該範圍時，賦In the composition (Q), the ratio of the polymerizable monomer (A) to the colloidal silica (B) is not particularly limited, and the colloidal polymer 2 (A) is 100 parts by mass based on the polymerizable monomer (A). The silicon oxide (B) (solid content) is preferably contained in an amount of 5 to 300 parts by mass, and more preferably contained in an amount of 10 to 200 parts by mass. When the ratio of colloidal silicon dioxide (B) is in the above range, the hard coat layer (X) formed is excellent in abrasion resistance, transparency, and mechanical strength when an external force is applied. When the ratio of colloidal silicon dioxide (B) is less than 5 parts by mass, the hard coat layer (X) tends to have poor abrasion resistance. On the one hand, when the ratio of colloidal silicon dioxide (B) exceeds 300 parts by mass, haze is easily generated in the hard coating layer (X), and when the optical disc is forcibly deformed by an external force, the hard coating layer (X) ) Easy to crack. -19- (16) (16) 200423109 The lubricating agent (c) is added to the over-product (Q), which collectively indicates the lubricating agent (C-τ) described below and other additives described later. With lubricant. In the composition (Q), the ratio of the 'polymerizable monomer (A) to the lubricating agent (C) is not particularly limited, and the lubricity is imparted to 100 parts by mass of the polymerizable monomer (A). The agent (C) is preferably from 0.001 to 100 mass parts, and more preferably from 0.1 to 5.0 mass parts. When the ratio of the lubricating agent (C) is within the above range, the surface of the hard coat layer (Fig. Χ) formed is excellent in lubricity and abrasion resistance. When the lubricating agent (C) is added to less than 0.01 part by mass, the 'hard coating layer (X) tends to have poor surface lubricity. On the one hand, when the lubricating agent (c) is added in an amount of more than 10 parts by mass, the hard coat layer (X) can be plasticized, and the wear resistance tends to decrease. The lubricant (C-T) is added to the composition (Q), and is selected from the parts (c-1) formed by the parts represented by the formula (1), and the parts represented by the formulas (2) to (5). A compound in which at least one of the formed sites (c-2) and active energy ray-curable functional groups (c-3) are contained in one molecule. -(S i R 1 R 2 0) m- (1) (wherein R 2 is an alkyl group having 1 to 8 carbon atoms, and any of phenyl groups, and m is an integer ranging from 1 to 1000.) -20- ( 17) 200423109 R3- Formula (2) Formula (3) Formula (4) Formula (5) CH 2CH20) x-CH2CH (CH3) 0) C (= 0) C u H 2 u 0) t- (in the above formula , R3 is an olefin group having 6 to 20 carbon atoms, 乂 and 丫 are integers of 5 to 10, U is an integer of 3 to 5, and seven is an integer of 丄 to 20.) Lubricant (C-T ), Having a portion (c-1) (hereinafter, simply referred to as a portion (^ · 1) °) formed by the portion represented by the above formula (1), so that the surface of the hard coat layer (X) formed is excellent in lubricity. Specifically, in the order shown below, when the coefficient of friction of the surface of the hard coating film (X) layer is measured, the coefficient of dynamic friction before and after the flex resistance test is ≦ 0.1 or less. In the above formula (1), R 2 may be the same or different in each siloxane unit. In regard to the part corresponding to the above formula (1), specifically, for example, a polydimethylpolysiloxane unit, a polymethylphenylpolysiloxane unit ', a polydiphenylpolysiloxane unit, and the like. The number indicating the degree of polymerization is an integer from 1 to 100, preferably an integer from 1 to 500. When m is within this range, the surface of the hard coating layer (X) is excellent in lubricity. When m exceeds 1 0 0, the viscosity becomes too high, and it is difficult to mix with other components of the composition (Q). In the composition (Q), the portion (c-1) formed by the lubricant-imparting agent (C -T) in the part represented by the formula (1) may be specified in different forms in the same molecule. There are more than two kinds. -21-(18) (18) 200423109 and 'composition (Q), in terms of imparting a lubricating agent (c-τ), a variety of additives having different positions (c-1) can be used. With lubricating agent (c-T). A part (c-2) (hereinafter referred to as a "part (c-2)") selected from the group consisting of at least one of the groups represented by the formulae (2) to (5) imparted with a lubricant (c-T). °) 'It has the function of showing compatibility with the polymerizable monomer (a). The part (c-1) to which the lubricating agent (c-T) is added has low affinity with the resin matrix formed by the polymerizable monomer (A), and therefore, it easily penetrates when the composition (Q) is hardened. Leakage on the surface of the resin matrix, which tends to impair the transparency of the hard coating (X) after hardening. The lubricating agent (C-τ) is added, and its part (c-2) is excellent in compatibility with the polymerizable monomer (A), although there is a part (c) having low affinity with the polymerizable monomer (a) -1), but also has a moderate compatibility with the polymerizable monomer (A). When the composition (Q) 'imparts a lubricant (C-T) to the polymerizable monomer (A) because it has moderate compatibility, the composition (Q) is applied to the surface of the film surface layer. When the transparency of the coating film before hardening is impaired, the lubricant (C · T) added to the coating film segregates on the surface of the coating film. Therefore, it does not impair the transparency of the hard coating (X) after hardening. The part represented by the above formula (2) has a linear or branched olefin group having 6 to 20 carbon atoms. When the carbon number is within this range, the compatibility of the lubricating agent (C · T) with respect to the polymerizable monomer (a) is moderate, and the crystallinity of the base is not too strong, so the hard coat layer (X) Surface lubricity and transparency-22- (19) 200423109 Excellent clarity. When the carbon number is 5 or less, the compatibility with the polymerizable monomer (A) is low, and the transparency of the coating film before curing is impaired. This will impair the transparency of the hard coating (X) after hardening. On the one hand, when the carbon number exceeds 20, the crystallinity of the base will be enhanced, or the transparency of the hard coat layer (X) will be impaired. The part represented by the above formula (3) represents a unit of ethylene oxide. X showing the degree of polymerization is an integer of 5 to 100. When X is in this range, assign

與潤滑性劑（C - T )，相對於聚合性單體（A )具有適 度相溶性，故硬塗層（X )表面潤滑性及透明性優異。X 較佳爲5〜8 0之整數。X爲4以下時，賦與潤滑性劑 (C - T )之相溶性低，會損及硬塗層（X )之透明性。 一方面，X超過1 0 0時，賦與潤滑性劑（C · T )之相 溶性過高，使得賦與潤滑性劑（C - T )難以在塗膜表面 偏析，使得硬塗層（X )無法顯現充分之表面潤滑性。Since it has moderate compatibility with the polymerizable monomer (A) and the lubricating agent (C-T), it has excellent surface lubricity and transparency of the hard coat layer (X). X is preferably an integer from 5 to 80. When X is 4 or less, the compatibility with the lubricating agent (C-T) is low, and the transparency of the hard coat layer (X) is impaired. On the one hand, when X exceeds 100, the compatibility with the lubricant (C · T) is too high, making it difficult for the lubricant (C-T) to segregate on the surface of the coating film, making the hard coating (X ) Cannot show sufficient surface lubricity.

上述式（4 )所示之部分，係表示環氧丙烷之單元。 顯示聚合度之y，爲5〜1 0 0之整數。y在該範圍時， 賦與潤滑性劑（C - T )，相對於聚合性單體（A )具有 適度相溶性，使得硬塗層（X )表面潤滑性及透明性優 異。y以5〜8 0之整數更佳。y在4以下時，賦與潤滑 性劑（C - T )之相溶性低，會損及硬塗層（X )之透明 性。一方面，y超過1 0 0時，賦與潤滑性劑（C - 丁） 之相溶性會過高，賦與潤滑性劑（C - T )會難以在塗膜 表面偏析，而無法充分顯現硬塗層（X )之表面潤滑性。 上述式（5 )所示之部分’表示內酯之開環體所得單 -23- (20) (20)200423109 元。該基之碳數由獲得之容易性爲3〜5之整數。又，表 示聚合度之t爲1〜20之整數。t在該範圍時，該基之 結晶性會過強，使硬塗層（X )之透明性優異。 賦與潤滑性劑（C - T )，在部位（C - 2 )方面，可 具有上述式（2)〜（5)所示部分中之任一種，或同一 分子内具有2種以上之部分。 組成物（Q )，在賦與潤滑性劑（C - T )方面，具 有不同部位（c - 2 )之賦與潤滑性劑（C - T )，可複數 種倂用。 在賦與潤滑性劑（C - T )中，所謂活性能量線硬化 性之官能團（c - 3 )(以下，稱爲官能團（c - 3 )。），若爲具有自由基反應性之官能團即可，具體而 言，以甲基丙烯醯基，烯丙基，乙烯基，乙烯醚基，鹵素 基，氫硫基等爲佳。就自由基反應性及所形成之化學鍵結 之穩定性而言，以甲基丙烯醯基特佳。 賦與潤滑性劑（C - T )，具有官能團（C-3 )，可使 組成物（Q )因活性能量線之照射而硬化之際，官能團 (c - 3 )亦產生硬化反應，而在組成物（Q )之硬化物 中與成爲樹脂基質之聚合性單體（A )成共價鍵結。藉 此，賦與潤滑性劑（C · T )，與組成物（Q )之硬化 物，亦即與硬塗層（X )藉由共價鍵結來鍵結，故不被固 定於硬塗層（X )表面之賦與潤滑性劑（C - T )並不存 在，因此並不會自硬塗層（X )之表面使得賦與潤滑性劑 (C - T )揮散，故較佳。又，賦與潤滑性劑（C - T )因 -24- (21) (21)200423109 與硬塗層（X )鍵結，經長期可顯現表面潤滑性。 賦與潤滑性劑（C - T )，在其分子内具有部位（C _ 1 )，部位（c - 2 )及官能團（c - 3 )。賦與潤滑性齊ij (C -T )中各部位之鍵結形態，並無特別限制。在賦與 潤滑性劑（C - T )中各部位之鍵結形態方面，具體而育 以以下之例爲佳。 1.直鏈型：部位（心1)，部位（0-2)及官能團（（：-3)連結成直線狀之形式。以下，稱爲直鏈型。 在該直鏈型中，於形成部位（c - 1 )之原料化合物 方面’可使用具有部位（c · 1 )之末端被羥基所改質之 化合物爲佳。例如，末端被羥基所改質之聚二甲基聚矽氧 院等爲佳。 因此，具有此等部位（c - 1 )之末端爲羥基所改質 之化合物之末端羥基’使得環氧乙烷，環氧丙烷，內酯等 之卓體聚合’鄰接於部位（C-1 )，而可構築部位（c· 2)。或者，在部位（c-2)方面，使用聚乙二醇’聚 丙二醇等聚合物之2官能異氰酸酯等，而可以烏拉坦鍵結 連結於部位（c -1 )。進而，具有部位（c · 1 )之末端 被羥基改質之化合物之末端羥基，使乙烯碳酸酯在觸媒存 在下’予以脫碳酸，並予加成，在插入環氧乙烷1單位之 上，使上述環氧丙烷，內酯等聚合，而可構築部位（c- 2 ) ° 目前爲止之操作，係部位（c - 2 )之末端爲羥基。 因此’在導入官能團（c-3)(例如，甲基丙烯醯基） -25- (22) 200423109 之方法方面，使用甲基丙烯酸，甲基丙烯酸氯化物等藉由 酯鍵結導入之方法，使用2 -甲基丙烯酸乙基異氰酸酯藉 由烏拉坦鍵結來導入之方法，而以藉由2 -羥基乙基甲基 丙烯酸酯，3 -羥基丙基甲基丙烯酸酯，4 -羥基丁基甲基 丙烯酸酯等之2官能異氰酸酯，以烏拉坦鍵結導入之方法 等爲佳。The part represented by the above formula (4) is a unit representing propylene oxide. The y of the polymerization degree is an integer from 5 to 100. When y is in this range, the lubricating agent (C-T) is added, and it has moderate compatibility with the polymerizable monomer (A), so that the surface of the hard coating layer (X) has excellent lubricity and transparency. y is more preferably an integer from 5 to 80. When y is 4 or less, the compatibility with the lubricant (C-T) is low, and the transparency of the hard coat layer (X) is impaired. On the other hand, when y exceeds 100, the compatibility with the lubricant (C-D) will be too high, and the lubricant (C-T) will be difficult to segregate on the surface of the coating film, and the hardness will not be fully developed. Surface lubricity of coating (X). The portion ′ shown by the above formula (5) represents a mono--23- (20) (20) 200423109 yuan obtained from a ring-opening body of a lactone. The easiness of obtaining the carbon number of the group is an integer of 3 to 5. In addition, t, which represents the degree of polymerization, is an integer of 1 to 20. When t is within this range, the crystallinity of the base is too strong, and the transparency of the hard coat layer (X) is excellent. The lubricating agent (C-T) may have any one of the parts represented by the formulae (2) to (5) in the part (C-2), or may have two or more kinds in the same molecule. The composition (Q) has a lubricating agent (C-T), and has a lubricating agent (C-T) having different positions (c-2), which can be used in plural kinds. In the lubricating agent (C-T), the so-called active energy ray-curable functional group (c-3) (hereinafter, referred to as a functional group (c-3)) is a functional group having a radical reactivity. Yes, specifically, a methacryl group, an allyl group, a vinyl group, a vinyl ether group, a halogen group, a hydrogen sulfide group, or the like is preferred. In terms of the radical reactivity and the stability of the chemical bonds formed, methacrylfluorenyl is particularly preferred. Lubricating agent (C-T) is added, and functional group (C-3) can harden the composition (Q) by irradiation of active energy rays. The functional group (c-3) also undergoes a hardening reaction. The hardened material of the composition (Q) is covalently bonded to the polymerizable monomer (A) serving as a resin matrix. As a result, the lubricating agent (C · T) and the hardened material of the composition (Q), that is, the hard coating (X) are bonded by covalent bonding, so it is not fixed to the hard coating. The lubricating agent (C-T) on the surface of the layer (X) does not exist. Therefore, the lubricating agent (C-T) is not allowed to be volatilized from the surface of the hard coating (X), so it is preferable. In addition, the lubricant (C-T) is bonded to the hard coat layer (X) due to -24- (21) (21) 200423109, and surface lubricity can be developed over a long period of time. The lubricating agent (C-T) is imparted with a site (C _ 1), a site (c-2), and a functional group (c-3) in the molecule. There is no particular limitation on the bonding morphology of the various parts in the lubricity uniform ij (C -T). Regarding the bonding morphology of each part of the lubricating agent (C-T), it is better to exemplify the following examples. 1. Straight-chain type: A site (heart 1), a site (0-2), and a functional group ((: -3) are connected in a linear form. Hereinafter, it is called a straight-chain type. In this straight-chain type, in For the raw material compound of the site (c-1), it is preferable to use a compound having a site (c · 1) whose end is modified by a hydroxyl group. For example, a polydimethylpolysiloxane whose end is modified by a hydroxyl group is used. Therefore, the terminal hydroxyl group of the compound modified with a hydroxyl group at the end of these sites (c-1) is such that the polymerization of ethylene oxide, propylene oxide, lactone, etc. is adjacent to the site (C -1) to construct the site (c · 2). Or, for the site (c-2), a bifunctional isocyanate such as a polymer such as polyethylene glycol and polypropylene glycol can be used, and it can be linked to the urethane bond. Site (c -1). Furthermore, a terminal hydroxyl group of a compound modified by a hydroxyl group at the end of the site (c · 1) is used to decarbonate ethylene carbonate in the presence of a catalyst, add it, and insert it into the ring. 1 unit of oxyethane, polymerizing the above-mentioned propylene oxide, lactone, etc. to form a site (c-2) ° In the operation so far, the terminal of the system site (c-2) is a hydroxyl group. Therefore, in the method of introducing a functional group (c-3) (for example, methacrylfluorenyl) -25- (22) 200423109, a methyl group is used Acrylic acid, methacrylic acid chloride, and the like are introduced by ester bonding, and 2-methacrylic acid ethyl isocyanate is introduced by urethane bonding, and 2-hydroxyethyl methacrylate is introduced. Bifunctional isocyanates such as 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and the like are preferably introduced by a method such as urethane bonding.

又，使用聚乙二醇，聚丙二醇等聚合物之一邊末端已 經甲基丙烯醯基改質之物，在與部位（c -1 )之末端之羥 基之間，使用2官能異氰酸酯等進行烏拉坦鍵結，在鄰接 於部位（c - 1 )，同時使部位（c - 2 )，官能團（c -3 )連結之方法亦較佳。 2.共聚合型：準備具有部位（c-Ι )之自由基聚合 性之巨合物與具有部位（c - 2 )之自由基聚合性之巨合 物，使該等巨合物共聚合後，導入官能團（c-3 )之型 式。以下，稱爲共聚合型。In addition, urethane is modified by using a bifunctional isocyanate or the like between one end of a polymer such as polyethylene glycol, polypropylene glycol, and the like having a methacryl group at the end. The method of bonding is adjacent to the site (c-1), and at the same time, the site (c-2) and the functional group (c -3) are connected. 2. Copolymerization type: prepare a radical polymerizable macro compound having a site (c-1) and a radical polymerizable macro compound having a site (c-2), and copolymerize these macro compounds Introducing the functional group (c-3). Hereinafter, it is called a copolymerization type.

在具有部位（c - 1 )之巨合物方面，以例如聚二甲 基聚矽氧烷之一邊末端爲甲基丙烯醯基所改質之物爲佳。 在具有部位（c - 2 )之巨合物方面，例如，聚乙二 醇，聚丙二醇等聚合物之一邊末端爲甲基丙烯醯基所改質 之物，甲基丙烯酸之烷基酯，內酯之開環聚合物之一邊末 端爲甲基丙烯醯基所改質之物等爲佳。 官能團（c - 3 )，有在使上述2種類之巨合物共聚 合後，在其末端導入之方法。例如，將上述2種巨合物之 甲基丙烯醯基並無加成者之末端羥基，使用甲基丙烯酸， -26- (23) (23)200423109 甲基丙烯酸氯化物等藉由酯鍵結導入之方法，以使甩2 -甲基丙烯酸乙基異氰酸酯，藉由烏拉坦鍵結導入之方法爲 佳。 或，與上述2種類之巨合物一起，使2 -羥基乙基甲 基丙烯酸酯，3-羥基丙基甲基丙烯酸酯，4-羥基丁基甲 基丙烯酸酯等共聚合之，其後有使用甲基丙烯酸，甲基丙 烯酸氯化物等藉由酯鍵結導入之方法，使用2 -甲基丙烯 酸乙基異氰酸酯藉由烏拉坦鍵結導入之方法。 又，在上述直鏈型及上述共聚合型之任一種中，官能 團（c - 3 )，以鄰接於部位（c - 2 )而鍵結者爲佳。官 能團（c - 3 )，在鄰接於部位（c - 2 )而鍵結之情形， 與鄰接於部位（c - 1 )而鍵結之情形比較，部位（c -1 ) 之表面移行性高，因此硬塗層（X )表面之潤滑性優異。 賦與潤滑性劑（C )，除了上述賦與潤滑性劑（C -T )以外可含有周知之賦與潤滑性劑。在此等周知之賦與 潤滑性劑方面，有例如聚矽氧烷油所代表之聚矽氧烷系賦 與潤滑性劑，氟系賦與潤滑性劑，脂肪酸酯蠟所代表之脂 肪酸酯系賦與潤滑性劑。但是，本說明書中周知之賦與潤 滑性劑，並不含有該當於上述賦與潤滑性劑（C - T )之 化合物。在含有該等賦與潤滑性劑之情形，相對於賦與潤 滑性劑（C )之合計質量1 〇 〇質量份爲含有5 0質量份 以下，較佳爲3 〇質量份以下。 在組成物（Q )中，活性能量線聚合引發劑（D )， 亦廣泛的含有周知之光聚合引發劑。在光聚合引發劑方 -27- (24) (24)200423109 面’尤其是以容易獲得之市售品爲佳。又，亦可倂用多種 光聚合引發劑。 在周知光聚合引發劑之具體例方面，有芳基酮系光聚 合引發劑（例如，苯乙酮類，二苯基酮類，烷基胺二苯基 酮類，苄基類，安息香類，安息香醚類，苄基二甲基縮酮 類，苯醯基苯甲酸酯類，a -醯基肟酯類等），含硫黄系 光聚合引發劑（例如，硫化物類，噻噸酮類等），醯基膦 氧化物系光聚合引發劑（例如，醯基芳基膦氧化物等）， 其他之光聚合引發劑等。又，該光聚合引發劑可與胺類等 之光増感劑組合使用。具體之光聚合引發劑方面，有例如 以下所舉出之化合物但並非僅限定於該等。 4-苯氧基二氯苯乙酮，4 -第三丁基二氯苯乙酮，4 -第三丁基三氯苯乙酮，二乙氧基苯乙酮，2-羥基-2-甲 基-1-苯基丙烷-1-酮，1-(4 -異丙基苯基）-2-羥基· 2 -甲基丙烷-1 -酮，1 - ( 4 -十二基苯基）-2 -甲基丙烷-1-酮，1-{ 4-(2-羥基乙氧基）苯基} - 2-羥基-2-甲 丙烷-1-酮’ 1-羥基環己基苯基酮，2-甲基-1-{4·(甲 基硫代）苯基} - 2 -嗎福林基丙烷-1 -酮。 安息香’安息香甲醚，安息香乙基醚，安息香異丙基 醚，安息香異丁基醚，苄基二甲縮酮，二苯基酮，苯醯基 安息香酸，苯醯基安息香酸甲酯，4-苯基二苯基酮，羥 基二苯基酮，丙烯基化二苯基酮，3.3’·二甲基-4-甲氧基 二苯基酮，3，3 ’，4，4 四個（第三丁基過氧羰基）二 苯基酮，9 ’ 1 0-菲醌，樟腦醌，二環庚酮，2 -乙基蒽 -28- (25) (25)200423109 醌，4·4·-二乙基間苯二甲醯基苯，1 -苯基-1，2·丙烷二酮-2 (鄰乙氧基羰基）肟，甲苯基乙醛酸酯。 4-苯醯基-4’ -甲基二苯基硫化物，噻噸酮，2-氯 噻噸酮，2 -甲噻噸酮，2 ，4 -二甲基噻噸酮，異丙基噻 噸酮，2 ，4 -二氯噻噸酮，2，4 -二乙基噻噸酮，2， 4 -二異丙基噻噸酮。 2，4，6 -三甲苯醯基二苯膦氧化物，苯醯基二苯膦氧 化物，2,6-二甲苯醯基二苯膦氧化物，雙（2，6 -二甲氧基 φ 苯醯基）-2 , 4，4 -三甲戊基膦氧化物。 在組成物（Q )中，活性能量線聚合引發劑（D )之 比例並無特別限定，通常相對於聚合性單體（A ) 100 質量份，以含有活性能量線聚合引發劑（D ) 0 · 0 1〜 2 0質量份者較佳，尤其是含有〇·1〜1 〇質量份者爲 佳。在該範圍時，組成物（Q )之硬化性爲充分，在硬化 之際，可使全部活性能量線聚合引發劑（D )分解故較 佳。 _ 因此，組成物（Q )，相對於聚合性單體（A ) 100質量份，以含有膠體狀二氧化矽（B) 5〜300 質量份，賦與潤滑性劑（C ) 0 · 0 1〜1 0質量份’及 活性能量線聚合引發劑（D ) 0 · 1〜2 0質量份爲特 佳。 在組成物（Q )，除了上述基本的成分以外可含有下 述之溶劑或各種其他機能性配合劑。 在組成物（Q )中使用溶劑之情形，以使用可溶解上 -29- (26) (26)200423109 述基本的成分之溶劑爲佳。又，依光碟基板之種類，選擇 適切溶劑使用爲佳，具體而言例如乙基醇，丁基醇，異丙 基醇等之低級醇類’甲基異丁基酮’甲基乙基酮，丙酮等 之酮類，一 π惡院，二乙二醇二甲基醚，四氫呋喃，甲基第 三丁基醚，對苯二酚單甲醚等之醚類，甲基溶纖劑，乙基 溶纖劑’丁基溶纖劑，丙二醇單甲醚乙酸酯等之溶纖劑類 等之有機溶劑爲佳。其他，亦可使用乙酸甲酯，乙酸乙酯， 乙酸丁酯’乙酸異戊酯，乳酸乙酯，琥珀酸二乙酯，己二 酸二乙酯，苯二甲酸二丁酯，苯二甲酸二辛酯等之二鹽基 酸酯等之酯類，氯化氟化烴類，三氯乙烷等之氯化烴類， 氟化烴類等之鹵化烴類，甲苯，二甲苯，己烷等之烴類等。 又’該溶劑之使用量，可依必要之組成物（Q )粘 度’目的之硬塗層（X )厚度，乾燥温度等條件等而適宜 變更。本發明中該溶劑，相對於聚合性單體（A )以使用 質量基準爲1 〇 〇倍以下，較佳爲〇.1〜5 〇倍之範圍爲 佳。 在上述之其他機能性配合劑方面，有選自紫外線吸收 劑，光穩定劑，氧化防止劑，熱聚合防止劑，塗平劑，消 泡劑，増粘劑，沈降防止劑，顔料（有機著色顔料，無機 顔料），著色染料，紅外線吸收劑，螢光増白劑，分散 劑，賦與防汚性劑，導電性微粒子，帯電防止劑，防曇 劑，偶合劑所成群之1種以上之機能性配合劑。 在紫外線吸收劑方面，作爲合成樹脂用紫外線吸收劑 以通常使用之苯并三唑系紫外線吸收劑，二苯基酮系紫外 -30- (27)200423109 線吸收 收劑等 之段落 (Q ) { 2 1 2 -羥3 基-5 -能團者 光 之受阻 268196 中，以 啶等之 在 阻酚（ 之磷系 醚等。 基樹脂 在 系消泡 聚合物 在 系有機 銘7 i目 ^ ’水楊酸系紫外線吸收劑，苯基三畊系紫外線吸 爲丫土。具體而g ’有日本特開平U-268196號公報 號碼0 〇 7 8所記載之化合物。本發明中，組成物 因含有多官能性之聚合性單體（a - 1 )，以在2 - 丨基- 5- ( 2-丙烯醯基氧乙基）苯基丨苯并三唑， •3-甲基丙烯醯基氧丙基-3- ( 3 -苯并三唑_4_羥 第二丁基苯基）丙酸酯等分子内具有光聚合性之官 特佳。 穩定劑方面，作爲合成樹脂用光穩定劑以通常使用 胺系光穩定劑爲佳。具體而言，有日本特開平n_ 5虎公報之段落號碼〇 〇 8 0所記載之化合物。本發明 N-甲基-4-甲基丙烯醯氧-2，2，6，6 -四甲基哌 分子内具有聚合性官能團之物特佳。 氧化防止劑方面，有2,6-二第三丁基對甲酚等之受 hindred phenol)系氧化防止劑，三苯基磷酸酯等 氧化防止劑等。熱聚合防止劑方面有對苯二酚單甲 又’塗平劑方面，有聚矽氧烷樹脂系塗平劑，丙烯 系塗平劑等。 消泡劑方面，有聚二甲基矽氧烷等之聚矽氧烷樹脂 劑等。又，増粘劑方面，有聚甲基甲基丙烯酸酯系 ’氫化蓖麻油系化合物，脂肪酸醯胺系化合物等。 有機著色顔料方面，有縮合多環系有機顔料，酞腈 顔料等。在無機顔料方面，有二氧化鈦，一氧化 紅，鈦黑等。又，著色染料方面，有有機溶劑可溶 -31 - (28) 200423109 性偶氮系金屬錯鹽染料，有機溶劑可溶性酞腈系染料等。 在紅外線吸收劑方面，有聚次甲基系，酞腈系，金屬 錯體系，銨系，二亞銨（diimonium )，蒽醌系，硫醇金 屬錯體系，萘醌系，吲哚酚系，偶氮系，三芳基甲烷系之 化合物等。 在賦與防汚性劑方面，有聚矽氧樹脂系防污添加劑， 氟樹脂系防汚添加劑等。In the case of a macro complex having a site (c-1), for example, a polydimethylsiloxane is modified with a methacryl group at one end of the polydimethylsiloxane. In terms of macro compounds having a site (c-2), for example, one end of polymers such as polyethylene glycol and polypropylene glycol is modified by a methacryl group, an alkyl ester of methacrylic acid, Ester ring-opening polymers are preferably modified with a methacryl group at one end. The functional group (c-3) is a method in which a macromolecular compound of the two types is copolymerized and then introduced at its terminal. For example, the methacryl fluorenyl group of the two types of macromolecules mentioned above has no terminal hydroxyl group, and methacrylic acid is used, and -26- (23) (23) 200423109 methacrylic acid chloride is bonded by ester The method of introduction is preferably a method of introducing 2-methyl methacrylate ethyl isocyanate by urethane bonding. Or, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and the like are copolymerized together with the above-mentioned two kinds of macro-composites, and then a formazan is used. The method of introducing methacrylic acid, methacrylic acid chloride, etc. by ester bonding, and the method of introducing 2-methacrylic acid ethyl isocyanate by urethane bonding. In either of the linear type and the copolymerized type, the functional group (c-3) is preferably adjacent to the site (c-2) and bonded. When the functional group (c-3) is bonded adjacent to the part (c-2), compared with the case where the functional group (c-1) is bonded, the surface (c-1) of the part has high migration. Therefore, the surface of the hard coating layer (X) has excellent lubricity. The lubricating agent (C) may contain a well-known lubricating agent in addition to the lubricating agent (C-T). As for these well-known lubricating agents, there are, for example, polysiloxane-based lubricating agents represented by polysiloxane oil, fluorine-based lubricating agents, and fatty acids represented by fatty acid ester waxes. Ester-based lubricant. However, the well-known lubricity-imparting agent in this specification does not contain a compound which is equivalent to the aforementioned lubricity-imparting agent (C-T). In the case where such a lubricity-imparting agent is contained, it is 50 mass parts or less, and preferably 30 mass parts or less, based on the total mass of the lubricating agent (C). In the composition (Q), the active energy ray polymerization initiator (D) also widely contains a well-known photopolymerization initiator. In terms of the photopolymerization initiator, -27- (24) (24) 200423109 is particularly preferably a commercially available product. In addition, a plurality of photopolymerization initiators may be used. Specific examples of well-known photopolymerization initiators include arylketone-based photopolymerization initiators (for example, acetophenones, diphenylketones, alkylamine diphenylketones, benzyls, benzoin, Benzoyl ethers, benzyl dimethyl ketals, phenylfluorenyl benzoates, a-fluorenyl oxime esters, etc., sulfur-containing yellow photopolymerization initiators (eg, sulfides, thioxanthone, etc.) ), Fluorenylphosphine oxide-based photopolymerization initiator (for example, fluorenylarylphosphine oxide, etc.), other photopolymerization initiators, and the like. The photopolymerization initiator can be used in combination with a photosensitizer such as an amine. Specific examples of the photopolymerization initiator include, but are not limited to, the compounds listed below. 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, 4-tert-butyltrichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl 1-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy · 2-methylpropane-1-one, 1- (4-dodecylphenyl)- 2-methylpropane-1-one, 1- {4- (2-hydroxyethoxy) phenyl}-2-hydroxy-2-methylpropane-1-one '1-hydroxycyclohexylphenyl ketone, 2 -Methyl-1- {4. ((Methylthio) phenyl) -2- 2-morpholinylpropane-1-one. Benzoin 'Benzoin methyl ether, Benzoin ethyl ether, Benzoin isopropyl ether, Benzoin isobutyl ether, Benzyl dimethyl ketal, Diphenyl ketone, Phenyl benzoic acid, Phenyl benzoin methyl ester, 4 -Phenyldiphenyl ketone, hydroxydiphenyl ketone, acrylated diphenyl ketone, 3.3 '· dimethyl-4-methoxydiphenyl ketone, 3,3', 4,4 four ( Third butylperoxycarbonyl) diphenyl ketone, 9 '1 0-phenanthrenequinone, camphorquinone, dicycloheptanone, 2-ethylanthracene-28- (25) (25) 200423109 quinone, 4 · 4 · -Diethyl m-xylylene benzene, 1-phenyl-1,2, propanedione-2 (o-ethoxycarbonyl) oxime, tolyl glyoxylate. 4-phenylfluorenyl-4'-methyldiphenylsulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone Tonone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone. 2,4,6-trimethylphenylfluorenyl diphenylphosphine oxide, phenylfluorenyl diphenylphosphine oxide, 2,6-xylylenediphenylphosphine oxide, bis (2,6-dimethoxy φ Phenylfluorenyl) -2,4,4-trimethylpentylphosphine oxide. In the composition (Q), the proportion of the active energy ray polymerization initiator (D) is not particularly limited, and it is usually contained in the active energy ray polymerization initiator (D) with respect to 100 parts by mass of the polymerizable monomer (A). · 1 to 20 parts by mass is preferable, and especially 0.1 to 10 parts by mass is preferable. In this range, the hardenability of the composition (Q) is sufficient, and it is preferable that all the active energy ray polymerization initiators (D) can be decomposed during hardening. _ Therefore, the composition (Q) is added with a lubricating agent (C) in an amount of 5 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A) and colloidal silica (B). 0 · 0 1 ~ 10 parts by mass' and the active energy ray polymerization initiator (D) 0 · 1 ~ 20 parts by mass are particularly preferred. The composition (Q) may contain, in addition to the above-mentioned basic components, the following solvents or various other functional compounding agents. When a solvent is used in the composition (Q), it is preferable to use a solvent that can dissolve the basic components described in -29- (26) (26) 200423109. In addition, depending on the type of the optical disc substrate, it is better to select a suitable solvent for use. Specifically, for example, lower alcohols such as ethyl alcohol, butyl alcohol, and isopropyl alcohol such as 'methyl isobutyl ketone' and methyl ethyl ketone. Ketones such as acetone, ethers such as 1π-cathode, diethylene glycol dimethyl ether, tetrahydrofuran, methyl tert-butyl ether, hydroquinone monomethyl ether, etc., methyl cellosolve, ethyl Organic solvents such as cellosolve butyl cellosolve, propylene glycol monomethyl ether acetate, and other cellosolvents are preferred. Alternatively, methyl acetate, ethyl acetate, butyl acetate 'isoamyl acetate, ethyl lactate, diethyl succinate, diethyl adipate, dibutyl phthalate, diphthalate Dibasic esters such as octyl esters, chlorinated fluorinated hydrocarbons, trichloroethane and other chlorinated hydrocarbons, fluorinated hydrocarbons and other halogenated hydrocarbons, toluene, xylene, hexane, etc. Hydrocarbons and so on. The amount of the solvent to be used may be appropriately changed depending on conditions such as the thickness of the hard coat layer (X) for the purpose of the required composition (Q) viscosity and the drying temperature. In the present invention, the solvent is preferably 1,000 times or less with respect to the polymerizable monomer (A) on a mass basis of use, and preferably in a range of 0.1 to 50 times. Among the other functional compounding agents mentioned above, there are selected from ultraviolet absorbers, light stabilizers, oxidation inhibitors, thermal polymerization inhibitors, leveling agents, defoamers, adhesives, sedimentation inhibitors, pigments (organic coloring) Pigments, inorganic pigments), coloring dyes, infrared absorbers, fluorescent whitening agents, dispersants, antifouling agents, conductive fine particles, anti-electrostatic agents, anti-moth agents, coupling agents Functional additives. In terms of ultraviolet absorbers, paragraphs (Q) of benzotriazole-based ultraviolet absorbers, diphenylketone-based ultraviolet-30- (27) 200423109, line absorbers, etc. are commonly used as ultraviolet absorbers for synthetic resins. In 2 1 2 -Hydroxy-3yl-5-groups, the light is blocked by 268196. Pyridine and other hindered phenols (such as phosphorus-based ethers, etc.). Resin-based antifoam polymers are used in organic systems. The salicylic acid-based ultraviolet absorber and the phenyl-three-cultivation ultraviolet absorber are yam soil. Specific examples include compounds described in Japanese Patent Application Laid-Open No. U-268196 No. 0 07. In the present invention, the composition contains Polyfunctional polymerizable monomer (a-1), in the 2-丨-5- (2-propenyloxyethyl) phenyl benzotriazole, 3-methylpropenyloxy Photo-polymerizable polymers, such as propyl-3- (3-benzotriazole_4-hydroxy second butylphenyl) propionate, are particularly preferred. As stabilizers, they are used as light stabilizers for synthetic resins. Generally, it is better to use an amine light stabilizer. Specifically, there is a chemical compound described in paragraph number 0800 of Japanese Unexamined Patent Publication No. 5 The N-methyl-4-methacrylofluorenyloxy-2,2,6,6-tetramethylpiperone having a polymerizable functional group in the molecule of the present invention is particularly preferable. As for the oxidation inhibitor, there are 2,6 -Hindred phenol) based oxidation inhibitors such as di-tert-butyl p-cresol, and oxidation inhibitors such as triphenyl phosphate. Examples of the thermal polymerization inhibitor include hydroquinone monolayers, and those of silicone resin-based levelers, acrylic-based levelers, and the like. As the antifoaming agent, there are polysiloxane resin agents such as polydimethylsiloxane. In addition, as the adhesive, there are polymethmethacrylate-based hydrogenated castor oil-based compounds, fatty acid amido-based compounds, and the like. Organic pigments include polycyclic organic pigments, phthalonitrile pigments, and the like. In terms of inorganic pigments, there are titanium dioxide, red oxide, and titanium black. In addition, as for coloring dyes, there are organic solvent-soluble -31-(28) 200423109 azo-based metal salt dyes, and organic solvent-soluble phthalonitrile-based dyes. In terms of infrared absorbers, there are polymethine-based, phthalonitrile-based, metal-based systems, ammonium-based, diimonium, anthraquinone-based, thiol metal-based systems, naphthoquinone-based, indolephenol-based, Azo-based, triarylmethane-based compounds, etc. In terms of imparting antifouling agents, there are polysiloxane resin antifouling additives and fluorine resin antifouling additives.

在導電性微粒子方面，有鋅，鋁，鎳等之金屬粉，磷 化鐵，銻滲雜型氧化錫等。 在帶電防止劑方面，有非離子系帯電防止劑，陽離子 帯電防止劑，陰離子系帯電防止劑等。 在偶合劑方面，有矽烷偶合劑，鈦酸酯偶合劑等。 在本發明中，硬塗層（X)之厚度以 //m爲佳，尤其是0.5〜10// m爲佳。在上述範圍時，該 硬塗層（X )之耐磨損性且機械強度優異。Examples of the conductive fine particles include metal powders such as zinc, aluminum, and nickel, iron phosphide, and antimony-doped tin oxide. As for the antistatic agent, there are non-ionic anti-electrolytic agents, cationic anti-electrolytic agents, and anionic anti-electrolytic agents. As for the coupling agent, there are a silane coupling agent, a titanate coupling agent, and the like. In the present invention, the thickness of the hard coating layer (X) is preferably // m, and particularly preferably 0.5 to 10 // m. Within the above range, the hard coat layer (X) is excellent in abrasion resistance and mechanical strength.

硬塗層（X )之厚度超過2 0 // m時，耐磨損性等表 面特性之提高無法期待更加提高，層會變脆，因光碟之些 微變形’亦會有在硬塗層（X)龜裂等產生之虞。又硬塗 層（X)之厚度不滿〇·1 /zm時，該硬塗層（X)之耐 磨損性有無法充分顯現之虞。 接著，就光碟基板加以説明。 在光碟基板方面，以在聚碳酸酯，聚甲基甲基丙烯酸 酯’非晶形聚烯烴等透明樹脂或玻璃上直接形成導溝之基 板，在上述透明樹脂或玻璃藉由光聚合物法來形成導溝之 -32- (29) 200423109 基板等爲佳。 在上述光碟基板之導溝表面，可形成下述之介電體 膜，記錄膜，反射膜等所成層合膜（記錄層）。該等各膜 之材質並無特別限定。 在介電體膜之材質方面，以例如，S i 3N4，S i 〇2， AlSi〇N，AlSiN，AIN，AITiN， Ta205，ZnS等爲佳。When the thickness of the hard coating layer (X) exceeds 2 0 // m, the improvement of surface properties such as abrasion resistance cannot be expected to be further improved. The layer will become brittle. Due to slight deformation of the optical disc, there will also be a hard coating layer (X ) The possibility of cracks and so on. When the thickness of the hard coating layer (X) is less than 0.1 / zm, the wear resistance of the hard coating layer (X) may not be sufficiently developed. Next, the optical disc substrate will be described. As for the optical disc substrate, a substrate is formed by directly forming a groove on a transparent resin such as polycarbonate, polymethylmethacrylate, amorphous polyolefin, or glass, and the transparent resin or glass is formed by a photopolymer method. -32- (29) 200423109 of the guide groove is preferred. On the surface of the groove of the above-mentioned optical disc substrate, a laminated film (recording layer) formed of a dielectric film, a recording film, a reflecting film, and the like described below can be formed. The material of each of these films is not particularly limited. In terms of the material of the dielectric film, for example, Si 3N4, Si 02, AlSiON, AlSiN, AIN, AITiN, Ta205, ZnS, etc. are preferred.

記錄膜之材質因記錄方式而異，例如，在追記型光記 錄媒體有T e ，S η，S e等硫族化合物系合金，相變化 型光記錄媒體有Te〇x，InSe，SnSb等硫族化合物 系合金，在光磁碟有TbFeCo ，NdDyFeCo等 過渡金屬與稀土類金屬之合金（單層或2層以上之交換鍵 結膜）爲佳。 反射膜之材質有例如，AI ，Au ，Ag，Cu等金 屬，Al-T i，Al-Cr等之合金爲佳。The material of the recording film varies depending on the recording method. For example, in the write-once optical recording medium, there are chalcogenide alloys such as T e, S η, and Se, and the phase-change optical recording medium includes sulfur such as TeOx, InSe, and SnSb. Group-compound alloys are preferably alloys of transition metals such as TbFeCo, NdDyFeCo and rare earth metals (single layer or two or more layers of exchange bond films) on the optical disk. The material of the reflective film is, for example, metals such as AI, Au, Ag, Cu, and alloys such as Al-Ti, Al-Cr are preferred.

本發明之光碟，例如可依以下方式製造。 在具有上述光碟基板之導溝之面，藉由常法來形成介 電體膜，記錄膜，反射膜等所成層合膜（記錄層）。介電 體膜’記錄膜及反射膜之各膜，可藉由潑濺法，離子電鍍 法等之物理蒸鍍法或等離子體C V D等之化學蒸鍍法來形 成。 在本發明中，在光碟之記錄層表面可形成薄膜表層。 在該薄膜表層之形成方法方面，藉由旋轉塗膜法，滾輪塗 敷法，網板印刷法等之塗布方法，將硬化性樹脂等予以均 -33- (30) 200423109 勻塗布後’藉由紫外線或電子線等之活性能量線照射所致 之硬化及/或熱硬化等來形成之方法，與將所定厚度之樹 脂薄膜藉由黏接層來貼合之方法等。The optical disc of the present invention can be manufactured in the following manner, for example. A laminated film (recording layer) made of a dielectric film, a recording film, a reflective film, or the like is formed on the surface having the guide groove of the optical disk substrate by a conventional method. Each of the dielectric film 'recording film and the reflective film can be formed by a physical vapor deposition method such as a sputtering method, an ion plating method, or a chemical vapor deposition method such as plasma CVD. In the present invention, a thin film surface layer may be formed on the surface of the recording layer of the optical disc. With regard to the method for forming the film surface layer, the hardening resin and the like are uniformly applied by a coating method such as a spin coating method, a roller coating method, and a screen printing method. (33) 200423109 After uniform coating A method of forming by hardening and / or thermal hardening caused by irradiation of active energy rays such as ultraviolet rays or electron beams, and a method of bonding a resin film of a predetermined thickness with an adhesive layer.

該薄膜表層’並無特別限定可採用周知或周知之方 法。例如，在上述所定厚度之樹脂薄膜方面，有擠塑 (cast )聚碳酸酯薄膜等。又該薄膜表層，可使用日本特 開平1 1 -240 1 03號公報之段落號碼〇〇24〜0〇36所記載之 多官能烏拉坦甲基丙烯酸酯化合物（以下，稱爲化合物 (E)。）來形成。在該化合物（E)方面，尤其是，以 2官能之化合物，質量平均分子量爲丨5 〇 〇以上，且，以 20000以下者爲佳。使用2官能之化合物，可使光聚合時 之硬化收縮量更低。又，採用上述範圍之質量平均分子 量，可調整薄膜表層形成用組成物之粘度於所望範圍，以 一次之塗膜可形成50/zm以上之層，同時，塗層作業會 變得容易。該化合物（E )可使用1種，亦可使用2種以 上。 該薄膜表層之厚度以 5〜200//m，40〜160/zm爲 佳。若於上述範圍內時，光碟之機械強度爲充分，且在資 料之記錄及播放，使用波長6 5 0 n m以下短波長雷射光之 際，傾斜之容許量或光碟之厚度不均勻之容許量爲充分的 大，而不會損及光碟之光學特性。又，就此層之厚度爲光 記錄播放裝置之光學設計而言被正確地決定爲要求値。 又，薄膜表層，可介在黏接層而設於記錄層上，在黏 接層方面，以紫外線硬化性之樹脂爲佳。又’該黏接層之 -34- (31) (31)200423109 厚度以〇·5〜50// m爲佳，尤其是1〜30# m爲佳。 在光碟之記錄層表面介在薄膜表層而形成上述硬塗層 (X )之方法方面，.並無特別限定，可採用公知乃至周知 之方法。例如，在將組成物（Q )塗布於薄膜表層面之方 法方面，可採用浸漬（dipping )法，流動塗膜法，噴塗 法，棒塗膜法，照相凹版塗膜法，滾輪塗膜法，刀片塗膜 法，氣刀塗膜法，旋轉塗膜法，槽（slit )塗膜法，微照 相凹版塗膜法等各種方法。 又’爲將組成物（Q )硬化以形成硬塗層（X )用之 活性能量線方面，以紫外線，電子線，X線，放射線及高 周波線寺爲佳，尤其是具有1 8 0〜5 0 0 n m之波長之紫外 線，較爲經濟。 在活性能量線源方面，可使用氙燈，低壓水銀燈，高 壓水銀燈，超高壓水銀燈，金屬鹵化物燈，碳弧燈，鎢燈 等之紫外線照射裝置，電子線照射裝置，X線照射裝置， 高周波產生裝置等。 本發明中光碟’可使用單片，亦可貼合2片以上使 用。又，可因應需要附有襯套，亦可組合於夾筒。 【實施方式】 〈實施例&gt; 以下’本發明係根據實施例（例1〜9 )，比較例 (例1 〇〜1 2 )加以説明，但本發明並不限定於該等。在 各例中’作爲光碟基材，係使用光碟基材1與光碟基材2 -35- (32) (32)200423109 〔光碟基材 1〕 在光記錄媒體.用聚碳酸酯基板（直徑1 2 c m，厚度 1 · 1 mm )之單面（具有導溝之面），將記錄層（A 1所 成反射膜，S iN所成第1介電體膜，TbFeCo所成 光磁記錄膜，S i N所成第2介電體膜）藉由潑濺法成膜 而形成。在該記錄層表面，作爲薄膜表層（V)，將帝人 公司製擠塑聚碳酸酯薄膜（商品名「PureAce」，厚度 7 0 #m)透過黏接層（厚度28//m)予以貼合。 〔光碟基材2〕 與光碟基材1爲相同構成，將記錄層中反射膜之形成 予以省略者作爲光碟基材2準備之。 關於各例中，係使用光碟基材爲相異之二個樣本來製 作’以以下所示方法進行各種物性之測定及評價，其結果 如表1所示。 又，在透明性’耐磨損性及4 0 0 n m光線透過率之測 定用樣本方面，係使用透明的光碟基材2，其他之物性之 測定，則使用反射膜所形成之光碟基材！。 〔透明性〕 關於樣本，係以霧度計測定四個地方之霧度値 (%) ’算出其平均値。樣本中硬塗層（X)之霧度係以 (樣本霧度値）-(光碟基材2之霧度値）之値（％ )表 -36- (33) (33)200423109 示0 〔耐磨損性〕 依照I s 0 9 3 5 2中所規定耐磨損試驗法’在2個 C S · 1 0 F磨損輪將各自5 0 〇 S之砝碼予以組合’旋 轉5 0 0次時之霧度値以霧度計來測定。霧度値之測定’ 係在磨損輪之循環軌道之四個地方進行’來測定平均値。 在耐磨損性方面，係以（磨損試驗後霧度値）-(初期霧 度値）之値（％ )表示。 | 〔4 0 0 n m光線透過率〕 藉由島津製作所公司製U V · 3 1 0 0，測定波長 4 0 0 n m中光線透過率。樣本中硬塗層（W )之透過率 係以（樣本之光線透過率）-(光碟基材2之光線透過 率）之値（％ )表示。 〔密接性〕 · 將樣本以剃刀之刃，以1 m m間隔切割出縦橫各爲 1 1條之裂縫，製作1 0 0個方格’以市售之類纖維素膠 帶（cellophane )予以良好密接後，在9 0度跟前方向急 遽彈出之際之，在薄膜表層及硬塗層不剝離而以残存之棋 盤方格之數（個）表示。 〔表面潤滑性〕 作爲表面潤滑性之指標，係使用Η E I D〇N公司製 -37- (34) (34)200423109The film surface layer 'is not particularly limited, and a known method or a known method can be used. For example, the resin film having the predetermined thickness mentioned above includes cast polycarbonate film and the like. As the film surface layer, a polyfunctional urethane methacrylate compound (hereinafter referred to as a compound (E)) described in Japanese Unexamined Patent Publication No. 1 1-240 1 03 can be used. ) To form. In terms of the compound (E), in particular, a bifunctional compound having a mass average molecular weight of 5,000 or more, and preferably 20,000 or less. By using a bifunctional compound, the hardening shrinkage during photopolymerization can be lowered. In addition, by using the mass average molecular weight in the above range, the viscosity of the composition for forming a thin film surface layer can be adjusted to a desired range, and a single coating film can be used to form a layer of 50 / zm or more. At the same time, the coating operation becomes easy. This compound (E) may be used alone or in combination of two or more kinds. The thickness of the surface layer of the film is preferably 5 to 200 // m, and preferably 40 to 160 / zm. If it is within the above range, the mechanical strength of the optical disc is sufficient, and when the short-wavelength laser light with a wavelength of less than 65 nm is used for recording and playback of the data, the allowable amount of tilt or uneven thickness of the optical disc is Large enough without compromising the optical characteristics of the disc. In addition, the thickness of this layer is accurately determined as a requirement in terms of the optical design of the optical recording and playback device. The film surface layer may be provided on the recording layer through the adhesive layer. As for the adhesive layer, a UV-curable resin is preferred. The thickness of the adhesive layer is -34- (31) (31) 200423109. The thickness is preferably from 0.5 to 50 // m, and particularly from 1 to 30 # m. There is no particular limitation on the method for forming the hard coat layer (X) on the surface of the recording layer of the optical disc through the film surface layer, and a well-known or well-known method can be adopted. For example, in the method of coating the composition (Q) on the surface layer of a thin film, a dipping method, a flow coating method, a spray coating method, a rod coating method, a gravure coating method, a roller coating method, Various methods, such as a blade coating method, an air knife coating method, a spin coating method, a slot coating method, and a microgravure coating method. For the active energy rays used to harden the composition (Q) to form the hard coat layer (X), ultraviolet rays, electron rays, X-rays, radiation, and high-frequency waves are preferred, especially those having 1 8 0 to 5 UV light with a wavelength of 0 0 nm is more economical. In terms of active energy ray sources, xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, and other ultraviolet irradiation devices, electron beam irradiation devices, X-ray irradiation devices, and high frequency generation can be used. Device, etc. In the present invention, a single disc may be used, or two or more discs may be bonded. In addition, a bushing can be attached as required, or it can be combined with a collet. [Embodiments] <Examples> Hereinafter, the present invention will be described based on examples (Examples 1 to 9) and comparative examples (Examples 1 to 12), but the present invention is not limited to these. In each example, as the optical disc substrate, the optical disc substrate 1 and the optical disc substrate 2 were used. (35) (32) (32) 200423109 [Disc substrate 1] In an optical recording medium, a polycarbonate substrate (diameter 1) was used. 2 cm, thickness 1 · 1 mm) on one side (the surface with the guide groove), the recording layer (a reflective film made of A 1, a first dielectric film made of SiN, and a magneto-optical recording film made of TbFeCo, The second dielectric film made of SiN is formed by a sputtering method. On the surface of this recording layer, as a film surface layer (V), an extruded polycarbonate film (trade name "PureAce", thickness 7 0 #m) manufactured by Teijin Corporation was bonded through an adhesive layer (thickness 28 // m). . [Disc base material 2] The same structure as that of the disc base material 1, and the formation of the reflection film in the recording layer is omitted as the disc base material 2 and prepared. In each of the examples, two samples with different disc substrates were used to produce the '. Various physical properties were measured and evaluated by the methods shown below. The results are shown in Table 1. In addition, in terms of the sample for measuring transparency 'abrasion resistance and light transmittance of 400 nm, a transparent disc substrate 2 is used. For other physical properties, a disc substrate formed by a reflective film is used! . [Transparency] For samples, the haze 値 (%) of four places was measured with a haze meter to calculate the average 値. The haze of the hard coating (X) in the sample is (Sample haze 値)-(Haze 値 of the disc substrate 2) (%) Table-36- (33) (33) 200423109 Shows 0 [resistant Abrasion resistance] According to the abrasion resistance test method specified in I s 0 9 3 5 2 'When two CS · 10 F wear wheels are combined with a weight of 50 0S each' when rotated 500 times Haze 値 is measured with a haze meter. The measurement of haze 値 is performed at four places of the cycle track of the wear wheel to measure the average 値. In terms of abrasion resistance, it is expressed as (%) of (haze 后 after abrasion test)-(initial haze 値). [4 0 0 n m light transmittance] The light transmittance at a wavelength of 4 0 n m was measured with U V · 3 1 0 0 manufactured by Shimadzu Corporation. The transmittance of the hard coating (W) in the sample is expressed by (%) of (light transmittance of the sample)-(light transmittance of the disc substrate 2). [Adhesiveness] · Cut the sample with 11 razor-shaped transverse cracks at 1 mm intervals with a razor blade, make 100 squares, and use a commercially available cellulose tape (cellophane) for good adhesion. Later, when it is suddenly ejected in the direction of 90 degrees, the surface layer of the film and the hard coating layer are not peeled off, but are represented by the number of remaining checkerboard squares. [Surface Lubricity] As an index of surface lubricity, ΗE I DON Corporation -37- (34) (34) 200423109 was used.

Slipping Tester H E l D〇N-14來測定硬塗層表面之 動摩擦係數。以表面潤滑性之持續性之指標，來測定耐摺 動性（接觸狀態下擦動）試驗後之動摩擦係數。所謂耐摺 動性試驗，係在温度50 ±2 °C，相對濕度50^5%之環境條 件下，將SONY公司製磁頭R F 3 2 0- 74 G相對於磁碟以 載重2 g之方式接觸之，在磁碟旋轉數600 r pm，使連 續進行5 00萬次旋轉者。 「原料化合物」 1 )聚合性單體（A ) 多官能性聚合性單體（a · 1 ) A 1:將含羥基之二新戊四醇聚丙烯酸酯與六亞甲基 二異氰酸酯反應所得每1分子之平均丙烯醯基數爲1 5 ， 分子量2 3 0 0之丙烯基烏拉坦。 A 2:二新戊四醇六丙烯酸酯。 單官能性聚合性單體（a -2) A 3 :異冰片基丙烯酸酯。 2 )活性能量線聚合引發劑（D ) D 1 : 2 -甲基-1-(4 -甲基苯硫基）-2 -嗎福林基-丙 烷-1 -酮。 3 )膠體狀二氧化矽（B ) B 1 :在乙基溶纖劑分散型膠體狀二氧化矽（二氧化 矽含量30質量％，平均粒徑11 nm) 10 0質量份， 添加3 -氫硫丙基三甲氧基矽烷2 · 5質量份，在8 0 °C加熱 (35) 200423109 攪拌5小時後，在室温下熟化1 2小時所得，在表面具有 含氫硫基之矽烷化合物之水解縮合物之膠體狀二氧化矽。 B 2:在丙二醇單甲醚乙酸酯分散型膠體狀二氧化矽 (二氧化矽含量3 0質量％，平均粒徑1 1 n m。）之Slipping Tester H E DON-14 was used to determine the dynamic friction coefficient of the hard coating surface. Using the continuous index of surface lubricity, the coefficient of dynamic friction after the flex resistance (friction in contact state) test was measured. The so-called bending resistance test is to contact the magnetic head RF 3 2 0- 74 G made by SONY company to the magnetic disk at a load of 2 g under the environmental conditions of temperature 50 ± 2 ° C and relative humidity 50 ^ 5%. In other words, the number of rotations of the disk is 600 r pm, and the number of consecutive rotations is 5 million. "Raw material compound" 1) polymerizable monomer (A) polyfunctional polymerizable monomer (a · 1) A 1: each obtained by reacting hydroxy-containing neopentaerythritol polyacrylate with hexamethylene diisocyanate Propylene urethane having an average number of acrylamide groups of 15 per molecule and a molecular weight of 2,300. A 2: Dinepentaerythritol hexaacrylate. Monofunctional polymerizable monomer (a-2) A 3: isobornyl acrylate. 2) Active energy ray polymerization initiator (D) D 1: 2-methyl-1- (4-methylphenylthio) -2 -morpholinyl-propane-1 -one. 3) Colloidal silicon dioxide (B) B 1: Colloidal silicon dioxide dispersed in ethyl cellosolve (silicon dioxide content 30% by mass, average particle size 11 nm) 100 parts by mass, 3-hydrogen added 2.5 parts by mass of thiopropyltrimethoxysilane, heated at 80 ° C (35) 200423109, stirred for 5 hours, and aged at room temperature for 12 hours, hydrolyzed and condensed with a thio compound containing hydrogen sulfide on the surface Colloidal silica. B 2: in propylene glycol monomethyl ether acetate dispersion type colloidal silica (silica content 30% by mass, average particle size 11 nm).

100質量份，添加3-甲基丙烯醯氧丙基三甲氧基矽烷 2·5 質量份，在5 0 °C攪拌3小時後，在室温予以熟化1 2小時 所得’表面具有含甲基丙烯醯基之矽烷化合物之水解縮合 物之膠體狀二氧化矽。 「賦與潤滑性劑（C - T )之合成」 以下所述之數平均分子量，藉由膠透層析法，以聚苯 乙烯爲標準物質所測定之値。 (C 1)在安裝有攪拌機之3 0 0rnL之四口燒瓶， 添加在二甲基聚矽氧烷油之兩末端有聚環氧丙烷之單元加 成之油（信越化學工業公司製X-22-4952，羥基價= 29, 數平均分子量約3870) 100 g與二月桂酸二丁基錫50 m g與2,6-二-第三丁基對甲酚2 5 〇 m g，在室温下攪拌 30分後’添加2 -甲基丙烯醯氧乙基異氰酸酯1 2 · 6g， 於室温進而攪拌24小時，得到兩末端被甲基丙烯醯基所 修飾之賦與潤滑性劑（C 1 ) 。C I之數平均分子量爲約 4200 〇 (c 2)在安裝有攪拌機及冷却管之300 mL四口燒 瓶’添加四異丁氧化鈦8 0 m g與一邊末端羥基之二甲聚 矽氧烷油（信越化學工業公司製X - 2 2 · 1 7 0 B X，羥基價 -39- (36) 200423109 8 .5，數平均分子量= 300 0) 100 g與ε-己內酉曰25 g 在1 5 0 °C加熱5小時，得到在二甲聚矽氧烷油之一邊末 端，ε -己內酯爲開環加成之白色蠟狀之化合物（己內酯 之聚合度=6 . 6 )。接著，將反應組成物冷卻至室温，100 parts by mass, 2.5 parts by mass of 3-methacrylic acid oxypropyltrimethoxysilane was added, and the mixture was stirred at 50 ° C for 3 hours, and then aged at room temperature for 12 hours to obtain 'the surface has methacrylic acid containing Colloidal silica of hydrolyzed condensate of silane compound. "Synthesis of lubricity-imparting agent (C-T)" The number average molecular weight described below was determined by gel permeation chromatography using polystyrene as a standard substance. (C 1) A 300-rnL four-necked flask equipped with a stirrer was added with a unit addition oil of polypropylene oxide at both ends of dimethyl polysiloxane oil (X-22 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) -4952, hydroxyl value = 29, number average molecular weight about 3870) 100 g and 50 mg of dibutyltin dilaurate and 250 mg of 2,6-di-tert-butyl-p-cresol, and stirred at room temperature for 30 minutes 'Add 2 · 6 g of 2-methacryl fluorenyl ethyl isocyanate, and stir at room temperature for 24 hours to obtain a lubricating agent (C 1) modified with a methacryl fluorenyl group at both ends. The number average molecular weight of CI is about 4,200 (c 2) In a 300 mL four-necked flask equipped with a stirrer and a cooling tube, 80 mg of tetraisobutyrate titanium oxide and a terminal hydroxy-dimethyl siloxane oil (Shin-Etsu X-2 2 · 1 7 0 BX manufactured by Chemical Industry Corporation, hydroxyl value -39- (36) 200423109 8 .5, number average molecular weight = 300 0) 100 g and ε-caproine 25 g at 150 ° C was heated for 5 hours to obtain a white waxy compound (ε-caprolactone polymerization degree = 6.6) at the end of one side of dimethyl polysiloxane oil, ε-caprolactone was a ring-opening addition. Next, the reaction composition is cooled to room temperature,

添加乙酸丁酯50 g與2,6-二-第三丁基對甲酚2 5 〇 m g， 攪拌約3 0分後，添加 2-甲基丙烯醯氧乙基異氰酸酯 5.05g在室温進而攪拌24小時，得到一邊末端被甲基丙烯 醯基所修飾之賦與潤滑性劑（C 2 )固形成分72 %之乙醆 丁酯溶液。C 2之數平均分子量爲，約3 7 5 0。 (C 3)在安裝有攪拌機及冷却管之3 00 mL之四口 燒瓶，添加2.2’-偶氮雙（2-甲基丙腈）600 m g與正十二 基硫醇7 4 0 m g與乙酸丁酯1 8 0 g，在室溫攪拌1 5分 後，添加一邊末端被甲基丙烯醯基所改質之二甲基聚矽氧 烷巨合物（信越化學工業公司製X-22-1 74DX，數平均分 子量5000) 4 5 g與聚環氧丙烷之一邊末端被丙烯醯基50 g of butyl acetate and 2,50 mg of 2,6-di-tert-butyl-p-cresol were added, and after stirring for about 30 minutes, 5.05 g of 2-methacryloxyethyl isocyanate was added and stirred at room temperature for 24 hours. Hours, a 72% solution of acetobutyl ester with a solid content of lubricating agent (C 2) modified by a methacryl group at one end was obtained. The number average molecular weight of C 2 is about 3 7 50. (C 3) In a 300 mL four-necked flask equipped with a stirrer and a cooling tube, add 2.2'-azobis (2-methylpropionitrile) 600 mg and n-dodecyl mercaptan 740 mg and acetic acid. 1 800 g of butyl ester was stirred at room temperature for 15 minutes, and then a dimethyl polysiloxane compound (X-22-1 manufactured by Shin-Etsu Chemical Co., Ltd.) modified by a methacryl group at one end was added. 74DX, number average molecular weight 5000) 4 5 g and one side of the polypropylene oxide is acrylyl

所改質之巨合物（日本油脂公司製 blenmeir-A P-800, C H 2=CHC〇〇-(CH 2 C Η ( C Η 3 )〇）y-H， y与13，羥基價= 66.8) 1 5 g ，在氮氣淸洗（purge) 後於70°C攪拌 聚合1 8小時。其結果得到數平均分子量 1 0000之聚合物。接著，將反應組成物冷卻至室温，添加 二月桂酸二丁基錫50 m g與2，6-二第三丁基對甲酚100 m g，在室温攪拌30分後添加2-甲基丙烯醯氧乙基異氰 酸酯2.27 g，在室温下，進而攪拌24小時得到共聚合物 之聚合單位之内聚環氧丙烷末端被甲基丙烯醯基所修飾之 -40- (37) 200423109 賦與潤滑性劑（C 3 )之固形成分約2 5 %之乙酸丁酯溶 液。C 3之數平均分子量爲約10450。Modified macro compound (blenmeir-A P-800, manufactured by Japan Oil Corporation, CH 2 = CHC〇〇- (CH 2 C Η (C Η 3) 〇) yH, y and 13, hydroxyl value = 66.8) 1 After 5 g of nitrogen purge, the mixture was stirred and polymerized at 70 ° C for 18 hours. As a result, a polymer having a number average molecular weight of 10,000 was obtained. Next, the reaction composition was cooled to room temperature, 50 mg of dibutyltin dilaurate and 100 mg of 2,6-di-tert-butyl-p-cresol were added, and after stirring at room temperature for 30 minutes, 2-methacryloxyethyl was added. Isocyanate 2.27 g, at room temperature, and then stirred for 24 hours to obtain the copolymerization unit of the copolymer. Polypropylene oxide terminal modified with methacryl group -40- (37) 200423109 Lubricant (C 3 ) Solid solution of about 25% butyl acetate solution. The C 3 number average molecular weight is about 10450.

(C 4)在安裝攪拌機及冷却管之300 mL之四口燒 瓶，添加2.2，-偶氮雙（2-甲丙腈）60 0 m g，正十二基硫 醇740mg，與乙酸丁酯1 80g，在室溫攪拌15分後’ 得到一邊末端爲甲基丙烯醯基所改質之二甲聚矽氧烷巨合 物（信越化學工業公司製X-22-1 74 DX，數平均分子量 5 000 ) 45 g與聚環氧丙烷之一邊末端被丙烯醯基所改質 之巨合物（日本油脂公司製Blenmer-AE-200，CH ι二 CHC〇〇-(C 2Η 4Οπ-Η ，η 与 4.5，經基價=1 7 4)(C 4) In a 300 mL four-necked flask equipped with a stirrer and a cooling tube, add 2.2-azobis (2-methylpropionitrile) 60 0 mg, n-dodecyl mercaptan 740 mg, and butyl acetate 1 80 g After stirring at room temperature for 15 minutes, a dimethylpolysiloxane macromolecule (X-22-1 74 DX, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) with a methacryl group at one end was obtained, and the number average molecular weight was 5,000. ) 45 g of a macro compound with one end of polypropylene oxide modified by an acrylyl group (Blenmer-AE-200, manufactured by Nippon Oil & Fats Co., Ltd., CH ι-CHC〇〇- (C 2Η 4〇π-Η, η and 4.5 , The base price = 1 7 4)

15 g，在氮氣淸洗後於7(TC進行18小時攪拌 聚合。 其結果得到數平均分子量1 0000之聚合物。接著，將反應 組成物冷卻至室温，添加二月桂酸二丁基錫5 0 m g與 2,6-二·第三丁基對甲酚100 mg，在室温攪拌30分後， 添加2 -甲基丙烯醯氧乙基異氰酸酯7.1 4 g，在室温進 而攪拌24小時，得到共聚合物之聚合單位之内聚環氧乙 烷末端被甲基丙烯醯基所修飾之賦與潤滑性劑（C 4 )之 固形成分約25%之乙酸丁酯溶液。C 4之數平均分子量 爲約1 1 200。 (C 5)在安裝攪拌機及冷却管之3 0 OmL之四口 燒瓶，添加2.2’·偶氮雙（2-甲基丙腈）6 0 Om g ，正十 二基硫醇7 4 0 m g，與乙酸丁酯1 8 0 g，在室温攪拌1 5 分後，添加一邊末端被甲基丙烯醯基所改質之二甲基聚矽 氧烷巨合物（信越化學工業公司製X -22- 1 74DX，數平均 -41 - (38) 20042310915 g was stirred and polymerized at 7 ° C. for 18 hours after being purged with nitrogen. As a result, a polymer having a number average molecular weight of 10,000 was obtained. Next, the reaction composition was cooled to room temperature, and 50 mg of dibutyltin dilaurate was added. 100 mg of 2,6-di · third-butyl-p-cresol was stirred at room temperature for 30 minutes, and then 7.14 g of 2-methacryloxyethyl isocyanate was added, and the mixture was further stirred at room temperature for 24 hours to obtain a copolymer. Within the polymerization unit, the end of the polyethylene oxide is modified with a methacryl group to give a lubricating agent (C 4) with a solid content of about 25% in a butyl acetate solution. The number average molecular weight of C 4 is about 1 1 200. (C 5) In a 300 mL four-necked flask equipped with a stirrer and a cooling tube, 2.2 ′ · azobis (2-methylpropionitrile) 6 0 Om g and n-dodecyl mercaptan 7 4 0 were added. mg, with 180 g of butyl acetate, stirred at room temperature for 15 minutes, and then added a dimethylpolysiloxane macromolecule modified at one end with a methacryl group (Xinyue Chemical Industry Co., Ltd. X- 22- 1 74DX, number average -41-(38) 200423109

分子量5000) 35 g與丙烯酸十八酯20 g，與2 -羥基乙 基丙烯酸酯5 g，在氮氣淸洗後於7 0 °C進行1 8小時攪 拌·聚合。其結果得到數平均分子量2 5 0 0 0之聚合物。接 著，將反應組成物冷卻至室溫，添加二月桂酸二丁基錫 50〇1§與2，6-二-第三丁基對甲酚1001118，在室温 攪拌30分後，添加2-甲基丙烯醯氧乙基異氰酸酯6 . 6 1 g，於室温下進而攪拌24小時，得到共聚合物之聚合單位 内2 -羥基乙基丙烯酸酯末端被甲基丙烯醯基所修飾之賦 與潤滑性劑（C 5 )之固形成分約2 5 %之乙酸丁酯溶液。 C 5之數平均分子量爲約28000。Molecular weight 5000) 35 g, 20 g of octadecyl acrylate, and 5 g of 2-hydroxyethyl acrylate were stirred and polymerized at 70 ° C for 18 hours after being purged with nitrogen. As a result, a polymer having a number average molecular weight of 25,000 was obtained. Next, the reaction composition was cooled to room temperature, and dibutyltin dilaurate 501§ and 2,6-di-third-butyl-p-cresol 1001118 were added. After stirring at room temperature for 30 minutes, 2-methylpropene was added. 6.6.1 g of ethoxyethyl isocyanate, and further stirred at room temperature for 24 hours to obtain a lubricating agent (2-hydroxyethyl acrylate terminal modified by a methacryl fluorene group) in the polymerization unit of the copolymer ( C 5) solid solution of about 25% butyl acetate solution. The C 5 number average molecular weight is about 28,000.

(C 6)在安裝有攪拌機及冷却管之300 mL之四口 燒瓶，添加2.2’-偶氮雙（2-甲基丙腈）600 m g與正十二 基硫醇7 4 0 m g，與乙酸丁酯1 8 0 g，在室温攪拌1 5分 後，添加一邊末端被甲基丙烯醯基所改質之二甲聚矽氧烷 巨合物（信越化學工業公司製X -2 2-174 DX，數平均分 子量5 000 ) 4 5 g，與不飽和脂肪酸羥基烷基酯修飾ε - 己內酯（Dicel化學公司製Plugcel FA 2 D，己內酯之 聚合度數=2) 1 5 g，氮氣淸洗後於70 °C進行18小時 攪拌 聚合。其結果得到數平均分子量3 5 000之聚合物。 接著，將反應組成物冷卻至室溫，添加二月桂酸二丁基錫 5 0 m g與2,6-二-第三丁基對甲酚l〇〇mg，在室温下攪 拌3 0分後，添加2 -甲基丙烯醯氧乙基異氰酸酯6 · 6 9 g ’ 進而在室温攪拌24小時，得到共聚合物之聚合單位之不 飽和脂肪酸羥基烷基酯修飾ε-己內酯末端被甲基丙烯醯基 -42- (39) 200423109 所修飾之賦與潤滑性劑（C 6 )之固形成分約2 5 %之乙酸 丁酯溶液。C 6之數平均分子量爲約3 9000。 (C 7)在二甲基矽氧烷油之兩末端，有聚環氧丙烷 之單元被加成之油（信越化學工業公司製X -22 -49 5 2，羥 基價=29，數平均分子量約3 8 7 0 )。不具有活性能量線 硬化性之官能團（C · 3 )之例。(C 6) In a 300 mL four-necked flask equipped with a stirrer and a cooling tube, add 2.2'-azobis (2-methylpropionitrile) 600 mg and n-dodecyl mercaptan 740 mg, and acetic acid. 1 800 g of butyl ester was stirred at room temperature for 15 minutes, and then a dimethylpolysiloxane macromolecule modified at one end by a methacryl group (X-2 2-174 DX manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added. , Number average molecular weight 5 000) 4 5 g, Modified ε-caprolactone with unsaturated fatty acid hydroxyalkyl ester (Plug FA 2 D, manufactured by Dicel Chemical Co., degree of polymerization of caprolactone = 2) 1 5 g, nitrogen After washing, the mixture was stirred and polymerized at 70 ° C for 18 hours. As a result, a polymer having a number average molecular weight of 35,000 was obtained. Next, the reaction composition was cooled to room temperature, 50 mg of dibutyltin dilaurate and 100 mg of 2,6-di-third-butyl-p-cresol were added, and after stirring at room temperature for 30 minutes, 2 was added. -Methacrylic acid oxyethyl isocyanate 6. 6 9 g ′, and further stirred at room temperature for 24 hours to obtain unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone at the end of the copolymer as a methacryl group -42- (39) 200423109 Modified butyl acetate solution with a solid content of lubricating agent (C 6) of about 25%. The C 6 number average molecular weight is about 39,000. (C 7) An oil having a unit of polypropylene oxide added to both ends of dimethylsiloxane oil (X-22 -49 5 2 manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value = 29, number average molecular weight About 3 8 7 0). Examples of functional groups (C · 3) which do not have active energy ray hardenability.

(C 8)在二甲聚矽氧烷油之兩末端有甲基丙烯醯基 被加成之油（信越化學工業公司製X-22-164 C，二甲基 聚矽氧烷單元之數平均分子量二5 000 )。不具有部位 (C - 2 )之例。 (C 9)兩末端甲基之二甲聚5夕氧院油（信越化學工 業公司製KF96-5 0 )。不具有部位（c -2 )及官能團（c -3)之例。(C 8) The methacryl group is added to both ends of the dimethyl polysiloxane oil (X-22-164 C manufactured by Shin-Etsu Chemical Industry Co., Ltd., the average number of dimethyl polysiloxane units Molecular weight two 5 000). Example with no part (C-2). (C 9) Dimethicone oil (KF96-50 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) at both terminal methyl groups. An example without a site (c-2) and a functional group (c-3).

-43- 200423109 (40) 表1 C1 直鍵型 CHrC (CH3) COOC2H4NHC〇- (0CH?CH (CH3)) r〇C3H6~ (S i (CH3) 20) tt-Si (CH3) r C3Hb0- (CH2CH (CH3) 0) rC0NHC?H40C0C (CH2) =CH2 ^1^=21, y=18 C2 直鍵型 CH3 (S i (CH3) 20) i (CH3)厂C3H60- (C (=0) C5H100)厂CONHC2H4OCOC (CH3) =CH? 1 m与38. 4, t 兰 6. 6 C3 共聚合型 -[CHrC (CH3) CO IP) ] r lCHrCHC0 IQ) ] r f 与 1.5, g与 3.0， IP) ； -〇C3H6- (S i (CH3) 20) b-S i (CH3) ?-C3H7 (m=60) IQ1 ; -CMCH2CH (CH31 01 厂C0WHC2MC0C (CH3) =CH2 (y=13) C4 共聚合型 -[CHrC (CH3) CO IP) ] r lCHrCHC0 (Q) ] r f^l. 5, g~7. 8 IP] ; -0C3Hr(Si (CH3)r0)m-Si (CH3)2-C3H7 (m=60) (Q) ; -0- (CH2CH20) rC0NHC2H40C0CH (CH3) =CH2 (x=4. 5) C5 共聚合型 -[CHrC (CH3) CO IP) ] r [CH2-CHC0 IQ) ] r ICH2-CHC0 iR) ] h-f与2. 9，g~25, h与 18 IP)'; -0C3Hr(Si (CH3)20)ro-Si (CH3) 2-C3H7 (m=60) iQ) ; -0C1BH37 IR) ； -och2ch2o-conhc2h4ococh (CH3) =ch2 C6 共聚合型 -[CH2-C (CH3) CO IP) ] r [CH2-CHC0 IQ] ] r i^5.3, g~25 IP1 ; -〇C3Hr(Si (CH3120)i ICH3)广C3H7 lm=60) IQ) ; -0C?H4-0-(C&lt;=0) C5H100) t-CONHCrH4OCOCH (CH3) =CH2 (t%2) C7 :無部位(c-3) HH0CH2CH (CH3))厂0C3Hr (Si (CH3) ?0)rSi (CH3) rC3H6〇- (CH2CH (CH3) 0)rH ni=21, y=18 C8 無部位(c-2) CH,=C (CH3) C0-0C3H6- (Si (CH3) 20! rSi !CH3! 2-C3H60-C0C !0Η3) =CH2 m~59. 5 C9 無部位(c-2) 部位(c-3) CH3-(Si (CH3)?0)m-Si (CH3)2-CH3-43- 200423109 (40) Table 1 C1 Straight bond type CHrC (CH3) COOC2H4NHC〇- (0CH? CH (CH3)) r〇C3H6 ~ (S i (CH3) 20) tt-Si (CH3) r C3Hb0- ( CH2CH (CH3) 0) rC0NHC? H40C0C (CH2) = CH2 ^ 1 ^ = 21, y = 18 C2 Straight bond type CH3 (S i (CH3) 20) i (CH3) factory C3H60- (C (= 0) C5H100 ) Factory CONHC2H4OCOC (CH3) = CH? 1 m with 38.4, t blue 6. 6 C3 copolymerization type-[CHrC (CH3) CO IP)] r lCHrCHC0 IQ)] rf and 1.5, g and 3.0, IP) ; -〇C3H6- (S i (CH3) 20) bS i (CH3)? -C3H7 (m = 60) IQ1; -CMCH2CH (CH31 01 factory C0WHC2MC0C (CH3) = CH2 (y = 13) C4 copolymerization type- [CHrC (CH3) CO IP)] r lCHrCHC0 (Q)] rf ^ l. 5, g ~ 7. 8 IP]; -0C3Hr (Si (CH3) r0) m-Si (CH3) 2-C3H7 (m = 60) (Q); -0- (CH2CH20) rC0NHC2H40C0CH (CH3) = CH2 (x = 4. 5) C5 copolymer type- [CHrC (CH3) CO IP)] r [CH2-CHC0 IQ)] r ICH2- CHC0 iR)] hf and 2.9, g ~ 25, h and 18 IP) '; -0C3Hr (Si (CH3) 20) ro-Si (CH3) 2-C3H7 (m = 60) iQ); -0C1BH37 IR ); -Och2ch2o-conhc2h4ococh (CH3) = ch2 C6 copolymer type-[CH2-C (CH3) CO IP)] r [CH2-CHC0 IQ]] ri ^ 5.3, g ~ 25 IP1; -〇C3Hr (Si ( CH3120) i ICH3) Guang C3H7 lm = 60) IQ) ; -0C? H4-0- (C &lt; = 0) C5H100) t-CONHCrH4OCOCH (CH3) = CH2 (t% 2) C7: No position (c-3) HH0CH2CH (CH3)) factory 0C3Hr (Si (CH3) ? 0) rSi (CH3) rC3H6〇- (CH2CH (CH3) 0) rH ni = 21, y = 18 C8 No part (c-2) CH, = C (CH3) C0-0C3H6- (Si (CH3) 20 ! rSi! CH3! 2-C3H60-C0C! 0Η3) = CH2 m ~ 59. 5 C9 No part (c-2) Part (c-3) CH3- (Si (CH3)? 0) m-Si (CH3) 2-CH3

〔例1〕 在安裝有攪拌機及冷却管之3 00 m L之四口燒瓶，放 入多官能性聚合性單體A 2 8 0 g ，賦與潤滑性劑C 1 1 · 〇 g，活性能量線聚合引發劑D 1 4 · 0 g，作爲熱聚 -44- (41) 200423109 合防止劑之氫醌單甲醚 1 . g ，及作爲溶劑之： (A C B t ) 6 5 . 0 g，在常温及遮光之狀態 小時使均勻化。接著一邊攪拌一邊緩慢添加膠體 矽B 1 7 5 . 0 g，進而在常温及遮光狀態，攪 予以均勻化。接著，作爲溶劑添加二丁基醚（D 6 5 · 0 g，在常温及遮光狀態下，攪拌1小時得 (Q &quot; ° 接著，使組成物（Q 1 )在光碟基材之薄膜表 由旋轉塗膜法塗工（濕厚度6 μ m )，在9 0 °C之 烤爐中保持1分鐘，除去溶劑後，在所得塗膜， 圍中，使用高壓水銀燈照射1 0 0 0 m J / c 3 00〜3 90 n m領域之紫外線累計能量量。）之 形成膜厚1 . 8 # m之透明硬化物層。藉此，得到 表面，黏接層/薄膜表層/硬塗層（結膜厚9 9.8 形成之樣本1。 使用本樣本就前述所舉之透明性，耐磨損性 n m光線透過率，密接性，表面潤滑性之項目予 結果如表3所不。 乙酸丁酯 ，攪拌1 狀二氧化 拌1小時 BE) 到組成物 層表面經 熱風循環 於空氣氛 m2 (波長 紫外線， 在記錄層 A m )所 ，400 以評價。 (42)200423109 表2 A B C D AcBt DBE 例1 A2:80g B1 :75g Cl:1. Og D1 :4. Og 65. Og 65. Og 例2 A2:80g B1 :75g C2:1. Og D1 :4. Og 65. Og 65. Og 例3 A2:80g B1 :75g C3:1. Og D1 :4. Og 65. Og 65. Og 例4 A2:80g B1 :75g C4:1. Og D1 :4. Og 65. Og 65. Og 例5 A2:80g B1 :75g C5:1. Og D1 :4. 〇g 65. Og 65. Og 例6 A2:80g B1 :75g C6:1. Og D1 :4. Og 65. Og 65： Og 例7 A1 : 80g B1 :75g Cl :1. Og D1 :4. Og 65. Og 65. Og 例8 A2:60g A3:20g B1 :75g C2:1. Og D1 :4. Og 65. Og 65. Og 例9 A2:80g B2:75g C2:1. Og D1 :4. Og 65. Og 65. Og 例10 A2:80g B1 :75g C7: i. Og D1 :4. Og 65. Og 65. Og 例11 A2:80g B1 :75g C8:1. Og D1 :4. Qg 65. Og 65. Og 例1 2 A2:80g B1 :75g C9:1· Og D1 :4. Og 65. Og 65. Og 表3 透明性 霧度(％) 耐磨損 性(％) 400nm光線 透過率(％) 密接性 (個） 表面潤滑性(動摩擦係數） 初期 耐摺動性試驗後 例1 0. 1 2. 7 90. S 100 0. 05 0. 07 例2 0· 2 2. 9 90. 7 100 0. 04 0. 06 例3 0. 2 2. 6 90. 0 100 0. 06 0. 07 例4 0· 1 2. 4 90. 4 100 0. 05 0.07 例5 0. 2 2. 5 90. 8 100 0. 06 0. 08 例6 0. 2 2.8 90. 9 100 0. 05 0. 06 例7 0· 2 2. 3 90. 0 100 0. 05 0.06 例8 0. 3 3.3 91. 0 100 0. 05 0.07 例9 0. 2 2.9 91. 2 100 0. 07 0.07 例10 0· 3 3.5 90.4 100 0. 05 0.70 #τ·ι，蝎 mil 1. δ Λ 4 0. ^ 0-7 Λ 0/. L 1G0 0. 04 Π i 1 U. I I 例12 3. 5 3.6 81. 5 100 0. 03 0. 85[Example 1] A 300 m L four-necked flask equipped with a stirrer and a cooling tube was placed with a polyfunctional polymerizable monomer A 2 80 g, and a lubricating agent C 1 1 · 0 g was added, and active energy Linear polymerization initiator D 1 4 · 0 g, as thermal poly-44- (41) 200423109 hydroquinone monomethyl ether 1. g, and as solvent: (ACB t) 6 5. 0 g, in If the room temperature and light-shielding state are small, the uniformity is achieved. Subsequently, colloidal silicon B 15.0 g was slowly added while stirring, and then homogenized at normal temperature and in a light-shielded state. Next, dibutyl ether (D 6 5 · 0 g) was added as a solvent, and the mixture was stirred for 1 hour at room temperature and a light-shielding state to obtain (Q &quot; °). Then, the composition (Q 1) was formed on a film surface of the optical disc substrate. A spin coater (wet thickness 6 μm) was kept in an oven at 90 ° C for 1 minute. After removing the solvent, the obtained coating film was surrounded by a high-pressure mercury lamp and irradiated with 1000 m J / c 3 00 ~ 3 90 nm cumulative energy in the ultraviolet range.) A transparent hardened material layer with a film thickness of 1.8 mm is formed. Thereby, the surface, adhesive layer / thin film surface layer / hard coating (conjunctival film thickness 9) 9.8 Formed sample 1. The results of the transparency, abrasion resistance, nm light transmittance, adhesion, and surface lubricity mentioned above in this sample are shown in Table 3. Butyl acetate, stirred 1 Oxidation mix 1 hour BE) to the surface of the composition layer through hot air circulation in an empty atmosphere m2 (ultraviolet wavelength, in the recording layer A m), 400 to evaluate. (42) 200423109 Table 2 ABCD AcBt DBE Example 1 A2: 80g B1: 75g Cl: 1. Og D1: 4. Og 65. Og 65. Og Example 2 A2: 80g B1: 75g C2: 1. Og D1: 4. Og 65. Og 65. Og example 3 A2: 80g B1: 75g C3: 1. Og D1: 4. Og 65. Og 65. Og example 4 A2: 80g B1: 75g C4: 1. Og D1: 4. Og 65. Og 65. Og example 5 A2: 80g B1: 75g C5: 1. Og D1: 4.0 g 65. Og 65. Og Example 6 A2: 80g B1: 75g C6: 1. Og D1: 4. Og 65. Og 65: Og Example 7 A1: 80g B1: 75g Cl: 1. Og D1: 4. Og 65. Og 65. Og Example 8 A2: 60g A3: 20g B1: 75g C2: 1. Og D1: 4. Og 65. Og 65. Og Example 9 A2: 80g B2: 75g C2: 1. Og D1: 4. Og 65. Og 65. Og Example 10 A2: 80g B1: 75g C7: i. Og D1: 4. Og 65. Og 65. Og Example 11 A2 : 80g B1: 75g C8: 1. Og D1: 4. Qg 65. Og 65. Og Example 1 2 A2: 80g B1: 75g C9: 1. Og D1: 4. Og 65. Og 65. Og Table 3 Transparency Haze (%) Abrasion resistance (%) Light transmittance at 400nm (%) Adhesiveness (a) Surface lubricity (dynamic friction coefficient) Example after initial flex resistance test 1 0. 1 2. 7 90. S 100 0. 05 0. 07 Example 2 0 · 2 2. 9 90. 7 100 0. 04 0. 06 Example 3 0. 2 2. 6 90. 0 100 0. 06 0. 07 Example 4 0 · 1 2. 4 90. 4 100 0. 05 0.07 Example 5 0. 2 2. 5 90. 8 100 0. 06 0. 08 Example 6 0. 2 2.8 90. 9 100 0. 05 0. 06 Example 7 0 · 2 2. 3 90. 0 100 0. 05 0.06 Example 8 0. 3 3.3 9 1. 0 100 0. 05 0.07 Example 9 0. 2 2.9 91. 2 100 0. 07 0.07 Example 10 0 · 3 3.5 90.4 100 0. 05 0.70 # τ · ι, scorpion mil 1. δ Λ 4 0. ^ 0 -7 Λ 0 /. L 1G0 0. 04 Π i 1 U. II Example 12 3. 5 3.6 81. 5 100 0. 03 0. 85

〔例2〜1 2〕 除了將例1之組成物（Q )中聚合性單體（A )，膠 體狀二氧化矽（B )，賦與潤滑性劑（C )變更爲表2所 記載之種類及量以外，其他與例1之組成物（Q )相同組 -46- (43) 200423109 成之組成物被製造，使用該組成物來製造與例1相同之樣 本，並就上述所舉之透明性，耐磨損性，4 0 0 n m光線透 過率，密接性，表面潤滑性之項目予以評價。結果如表3 所示。 〈産業上之利用可能性&gt;[Examples 2 to 12] Except changing the polymerizable monomer (A) and colloidal silica (B) in the composition (Q) of Example 1 to the lubricating agent (C) as described in Table 2 Except for the type and amount, other components (46) (43) 200423109 which are the same as the composition (Q) of Example 1 are manufactured, and the same sample as in Example 1 is manufactured using this composition, and The items of transparency, abrasion resistance, light transmittance at 400 nm, adhesion, and surface lubricity were evaluated. The results are shown in Table 3. <Industrial possibilities>

依照本發明，係提供-種光碟，其在基板之表面，記 錄層與薄膜表層爲依此順序層合者，用於資料之記錄及/ 或播放之藍色雷射所代表之短波長之雷射光通過薄膜表層 照射於記錄層型式之光碟，在該薄膜表層之表面，耐磨損 性及長期之表面潤滑性優異，且透明性亦良好之硬塗層。 【圖式簡單説明】 第1圖：爲本發明一實施例之光碟剖面模式圖。According to the present invention, there is provided an optical disc having a short-wavelength laser represented by a blue laser for data recording and / or playback on a substrate surface, a recording layer and a thin film surface layer laminated in this order. The light is irradiated to the optical disc of the recording layer type through the thin film surface layer. On the surface of the thin film surface layer, the hard coating layer is excellent in abrasion resistance and long-term surface lubricity and has good transparency. [Brief description of the drawings] FIG. 1 is a schematic cross-sectional view of an optical disc according to an embodiment of the present invention.

符號之説明 1 :基板 2 :導溝 3 :記錄層 4 :薄膜表層 5 :硬塗層（X ) 6 :光碟 47-Explanation of symbols 1: Substrate 2: Guide groove 3: Recording layer 4: Thin film surface layer 5: Hard coating (X) 6: Optical disc 47-

Claims (1)

200423109 拾’ 〜2 之記 錄層 (X 合性 化矽 發劑 所成 (Q 及甲 以上 上， 式（ 〜（ 與活 劑（ (1) •申請專利範圍 1· 一種光碟，其特徵爲，在基板面，記錄層與厚度5 0 0 //. m之薄膜表層，依此順序層合者，使用於資料 錄及/或播放之雷射光通過該薄膜表層在照射於該記 方式之光碟中，於該薄膜表層上，形成硬塗層 )，該硬塗層（X )係含有，活性能量線硬化性之聚 單體（A)，平均粒徑1〜200n m之膠體狀二氧 (B )，賦與潤滑性劑（C )，與活性能量線聚合引 (D )，之活性能量線硬化性組成物（Q )之硬化物 者， 但是，該聚合性單體（A )，在含於該硬化性組成物 )之該聚合性單體（A )之總質量中，選自丙烯醯基 基丙烯醯基所成群之聚合性官能團1分子中具有2個 之多官能性聚合性單體（a - 1 )爲2 0質量％以 該賦與潤滑性劑（C )係含有，1分子中，選自下述 1 )所示部分所成部位（c - 1 )，與下述式（2 ) 5 )所示部分所成群之至少-種所成部位（c - 2 )， 性能量線硬化性之官能團（c - 3 )，之賦與潤滑性 C -T )， -(S i R 1 R 2〇 ) m- 式（1 ) (式中，R \R 2爲碳數1〜8之烷基或苯基之任-200423109 Pick up '~ 2 of the recording layer (made of X-type synthetic silicon hair agent (Q and A above), formula (~ (and active agent (1) • Patent application scope 1 · A type of optical disc, characterized in that The substrate surface, the recording layer and the film surface layer with a thickness of 5 0 0 //. M are laminated in this order. The laser light used for data recording and / or playback passes through the film surface layer and is irradiated on the disc in the recording mode. A hard coating layer is formed on the film surface layer), and the hard coating layer (X) is a colloidal dioxygen (B) containing an active energy ray-curable polymer monomer (A) and an average particle diameter of 1 to 200 nm. Those who impart a lubricating agent (C) with the active energy ray polymerization initiator (D), a hardened product of the active energy ray hardening composition (Q), but the polymerizable monomer (A) is contained in In the total mass of the polymerizable monomer (A) of the curable composition), a polyfunctional polymerizable monomer having two polymerizable functional groups selected from the group consisting of acrylfluorenyl and acrylfluorenyl groups has two (A-1) is 20% by mass and is contained in the lubricating agent (C), and 1 molecule is selected from the following 1) The formed site (c-1), at least one species formed site (c-2) grouped with the part represented by the following formula (2) 5), the functional group (c-3) of hardenability , Which imparts lubricity C -T),-(S i R 1 R 2〇) m- Formula (1) (where R \ R 2 is any alkyl or phenyl group having 1 to 8 carbon atoms- -48 (2) (2)200423109 種，m爲1〜1 〇 〇 〇之整數。） - 式 ( 2 ) -( C Η 2CH20 ) x - 式 ( 3 ) - C C Η 2 C Η ( CH3)〇)y- 式 ( 4) -( C ( =0 ) C u H 2 u 0 ) t - 式 ( 5 ) (上述式中，R3爲碳數6〜2 0之烯烴基，\及7 爲5〜1〇〇之整數，u爲3〜5之整數，t爲1〜20 之整數）。 2 ·如申請專利範圍第1項之光碟，其中，相對於該聚 合性單體（A ) 1 〇 〇質量份，平均粒徑1〜200 n m之 膠體狀二氧化砂（B ) 5〜3 0 0質量份，賦與潤滑性劑 (C )爲0 . 0 1〜1 〇質量份，及活性能量線聚合引發 劑（D )爲0 · 〇 1〜2 0質量份。 3 ·如申§靑專利範圍第1或2項之光碟，其中，該膠體 狀二氧化矽（B )以，具有氫硫基之有機基與水解性基及 /或羥基，爲鍵結於矽原子之含氫硫基之矽烷化合物被表 面修飾所得修飾膠體狀二氧化矽者。 4 ·如申請專利範圍第3項之光碟，其中該含氫硫基之 矽烷化合物係，下述式（6 )所示之化合物， HS-R-S i X lR °3.l 式（6) (式中，R表示烯烴基，R 0表示烷基，X表示羥基 -49- (3) (3)200423109 或水解性基，L表示1〜3之整數）。 5 ·如申請專利範圍第i或2項之光碟，其中，該膠體 狀一氧化矽（B )係，具有甲基丙烯醯基之有機基與水解 1生基及/或羥基，爲鍵結於矽原子之含有甲基丙烯醯基之 石夕院化合物被表面修飾所得之修飾膠體狀二氧化矽。 6·如申請專利範圍第5項之光碟，其中，該含有甲基 丙烯醯基之矽烷化合物爲，下述式（7 )所示之化合物， CH 2=CH (R 5) COO-R-s iXL R°3-l,式（7) (式中，R 5表示氫原子或甲基，R表示烯烴基， R 0表不院基’ X表不經基或水解性基，L表示1〜3之 整數）。 7 ·如申請專利範圍第1項至第6項之任一項之光碟，其-48 (2) (2) 200423109 species, m is an integer from 1 to 100. )-Formula (2)-(C Η 2CH20) x-Formula (3)-CC Η 2 C Η (CH3) 〇) y- Formula (4)-(C (= 0) C u H 2 u 0) t -Formula (5) (In the above formula, R3 is an olefin group having 6 to 20 carbons, \ and 7 are integers of 5 to 100, u is an integer of 3 to 5, and t is an integer of 1 to 20) . 2. The optical disc according to item 1 of the scope of patent application, wherein the colloidal sand dioxide (B) having an average particle diameter of 1 to 200 nm relative to 100 parts by mass of the polymerizable monomer (A) is 5 to 30. 0 parts by mass, the lubricating agent (C) is 0.01 to 10 parts by mass, and the active energy ray polymerization initiator (D) is 0. 〇1 to 20 parts by mass. 3. The optical disc of item 1 or 2 as claimed in § 靑, wherein the colloidal silicon dioxide (B) is bonded to silicon with an organic group having a hydrogen sulfur group and a hydrolyzable group and / or a hydroxyl group. Modified colloidal silica with atomic hydrogen sulfide-containing silane compounds modified by surface modification. 4. The optical disc according to item 3 of the scope of patent application, wherein the silane compound containing hydrogen sulfur group is a compound represented by the following formula (6), HS-RS i X lR ° 3.l Formula (6) (formula In the formula, R represents an olefin group, R 0 represents an alkyl group, X represents a hydroxy-49- (3) (3) 200423109 or a hydrolyzable group, and L represents an integer of 1 to 3). 5. The optical disc according to item i or 2 of the scope of patent application, wherein the colloidal silicon monoxide (B) system, an organic group having a methacryl group, and a hydrolyzable primary group and / or a hydroxyl group are bonded to Modified colloidal silicon dioxide obtained by surface modification of a silicon atom-containing methacrylium-based Shixianyuan compound. 6. The optical disc according to item 5 of the scope of patent application, wherein the methacryl group-containing silane compound is a compound represented by the following formula (7), CH 2 = CH (R 5) COO-Rs iXL R ° 3-l, formula (7) (where, R 5 represents a hydrogen atom or a methyl group, R represents an olefin group, R 0 represents a radical group, X represents a radical or a hydrolyzable group, and L represents 1 to 3 Integer). 7 · If the optical disc of any one of items 1 to 6 of the scope of patent application,
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